CN103456930B - Negative electrode diachylon used for high-performance AGM battery and preparing method thereof - Google Patents
Negative electrode diachylon used for high-performance AGM battery and preparing method thereof Download PDFInfo
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- CN103456930B CN103456930B CN201310444445.4A CN201310444445A CN103456930B CN 103456930 B CN103456930 B CN 103456930B CN 201310444445 A CN201310444445 A CN 201310444445A CN 103456930 B CN103456930 B CN 103456930B
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- agm
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- carbon black
- lead plaster
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- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000006071 cream Substances 0.000 claims description 35
- 239000011505 plaster Substances 0.000 claims description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 20
- 239000000654 additive Substances 0.000 claims description 18
- 230000000996 additive effect Effects 0.000 claims description 18
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 18
- 239000006229 carbon black Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 8
- 239000004021 humic acid Substances 0.000 claims description 8
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 230000008961 swelling Effects 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 2
- 230000019635 sulfation Effects 0.000 abstract description 6
- 238000005670 sulfation reaction Methods 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 239000003610 charcoal Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 206010011906 Death Diseases 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000004567 concrete Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- 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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of lead storage batteries and relates to a negative electrode diachylon which is capable of improving dynamic charging acceptance performance of an AGM battery and a preparing method thereof. The negative electrode diachylon is capable of improving the dynamic charging acceptance performance of the AGM battery under the condition that the AGM battery has the advantages of being long in service life and strong in starting capacity, the probability of sulfation of a negative plate when the negative plate is in a partial charge state for a long time is reduced, and then starting and shut-down requirements are met.
Description
Technical field
The invention belongs to lead accumulator technical field, relate to a kind of high-performance AGM negative electrode battery lead plaster and preparation method thereof, be specifically related to a kind ofly improve the dynamic charging of AGM battery cathode lead plaster and preparation method thereof by characteristic.
Background technology
Energy-conserving and environment-protective are developing direction of future automobile.Making laws in Europe, plans at CO by automobile in 2015
2discharge capacity is reduced to below 120g/km (higher than the Europe IV standard), this makes European all automobile production producers have to take new emission-reducing system and auxiliary power unit, and adopt stop/start(to start to stop) micro hybrid vehicle of system, only need carry out less improvement to automobile electric appliance system, generator on existing automobile is changed into and starts/generator, increase a set of stop/start(and start stopping) management system, adopt high power, long-life new A GM battery (lead acid accumulator), integral vehicle cost increases on a small quantity, under just can be implemented in municipal highway situation, reduce the CO of 3%-8%
2discharge capacity, the effect of fuel-economizing 3%-5% is market acceptance and the fabulous scheme of generalization in following 10-20.
So-called start-stop technology is fast exactly vehicle block up or etc. red light time automatically kill engine, the now electric equipment of automobile, Source Music and satellite navigation system etc. provide electric power by battery; Automatically can pilot engine rapidly again when driver steps on clutch, throttle or loosens the brake, provide power start engine by battery; And the energy produced instantaneously when working as automobile downhill or bring to a halt can change into rapidly electric energy is accepted by battery.Even if under these all require that the frequent use of battery is in partial state of charge, enough electricity, good flash-over characteristic also will be had; There is excellent charge characteristic simultaneously, high magnification charging current can be accepted, namely there is good dynamic charge acceptance.
Traditional AGM battery has the advantages that the life-span is long, starting capability is strong, but when being applied to start-stop automobile, under being in Partial charge state for a long time, very easily there is sulfation in negative plate, charging is subject to poor-performing by the especially dynamic charging of performance, battery is end-of-life because charging difficulty, is difficult to meet parking requirement.
Zhao Jiequan etc. (the progress .J. storage battery of hybrid vehicle analysing valve control type lead-acid accumulator battery negative pole carbonaceous additive, 2010,47 (05)) describe the up-to-date Recent Progresses In The Development that hybrid vehicle analysing valve control type lead-acid accumulator battery negative pole adds carbon.The article pointed out that adding high level material with carbon element makes moderate progress to performances of the lead-acid battery, as increased conductivity, lead sulfate is evenly distributed, increase specific area, reduce polarization, increase electric capacity effect etc., also indicate and add some adverse influences after carbon, in cathode lead plaster, directly add a large amount of carbon as pointed out and easily cause coming off of lead plaster in cyclic process, reduce the life-span of battery.So just have a strong impact on the normal use of lead acid accumulator in auxiliary products.
Chinese patent CN102074744B discloses a kind of plumbous charcoal super accumulator containing plumbous carbon composite, containing the plumbous carbon composite with high specific capacitance in the negative electrode active material of this plumbous charcoal super accumulator.The negative material of plumbous charcoal superbattery comprises the lead of 1-75% weight portion, the plumbous carbon composite of the high specific capacitance of 2-95% weight portion and the additive of 1.5-5% weight portion.The plumbous charcoal superbattery production process that the present invention proposes is few, internal structure is simple, cost is low, and cathode lead plaster is not easy to come off, and uses cycle life longer.But when being applied to start-stop automobile, still existing under being in Partial charge state for a long time, very easily there is sulfation in negative plate, and charging is subject to poor-performing by the especially dynamic charging of performance, battery is end-of-life because charging difficulty, is difficult to meet the problem of stopping and requiring.
Summary of the invention
The object of the present invention is to provide one can be applicable to start-stop automobile AGM battery cathode lead plaster, this cathode lead plaster can make AGM battery when having the advantage that the life-span is long, starting capability is strong, improve dynamic charging by performance, reduce and be in the situation that sulfation very easily occurs negative plate under Partial charge state for a long time, met parking requirement further.Be with traditional AGM battery difference, for meeting high magnification charging, electric discharge, long-life demand under start-stop automobile partial state of charge, especially brake energy reclaims function, reduce battery sulfation and improve charging by performance, even if the low specific surface area conventional carbon black that raising is many again or acetylene black can not meet parking instructions for use, and improving charging by the decline that may bring the performance such as accumulator drive, water consumption while performance.
Above-mentioned purpose is achieved by following technical solution:
A kind of high-performance AGM negative electrode battery lead plaster, is made up of the material of following weight unit's: lead powder 90-110 part, barium sulfate 0.2-2 part, mixing organic expander 0.1-3 part, mixing carbonaceous additive 0.1-4 part, sulfuric acid 2-10 part and water 9-18 part; PbO containing mass fraction 75-85% in described lead powder.
Preferably, a kind of high-performance AGM negative electrode battery lead plaster, be made up of the material of following weight unit's: 100 parts, lead powder, barium sulfate 0.4-1 part, mixing organic expander 0.4-1 part, mixing carbonaceous additive 0.2-2 part, sulfuric acid 3-7 part and water 10-15 part, preferred water is pure water.
Wherein, mix carbonaceous additive to be made up of the low specific surface area conductive carbon black of high-specific surface area carbon black and 0.1-1 part in 0.1-1 part.Middle high-specific surface area carbon black refers to that specific area is 200-2000m
2the carbon black of/g; Low specific surface area conductive carbon black refers to that specific area is less than 100m
2/ g, the carbon black of resistivity≤1.8 Ω m.
Middle high-specific surface area carbon black in above-mentioned mixing carbonaceous additive and the mass ratio of low specific surface area conductive carbon black are preferably 1:1-1:3.Test shows, the amount that mixing carbon adds and ratio very important, excessive carbon can cause battery because liberation of hydrogen is serious, water consumption increases and end-of-life, the charging that unfavorable ratio can affect battery on the contrary by, start and the life-span.
Mixing organic expander is that the humic acid of 16:1-1:1 and sodium lignosulfonate form by mass ratio; Being preferably by mass ratio is that the humic acid of 8:1-3:2 and sodium lignosulfonate form.
It is 1.2-1.8g/cm that sulfuric acid is preferably density
3the sulfuric acid of (25 DEG C), more preferably density is 1.39-1.49g/cm
3the sulfuric acid of (25 DEG C), concrete preferably density is 1.4g/cm
3the sulfuric acid of (25 DEG C).
The invention provides a kind of high-performance AGM battery, this battery adopts technique scheme gained cathode lead plaster.
Another object of the present invention is to provide a kind of preparation method of above-mentioned start-stop AGM battery terminal negative lead plaster, and step is as follows:
1) water mixes swelling agent and carbonaceous additive:
By mixed expanded dose with mix carbonaceous additive and add water and stir, obtain water and mix swelling agent and carbonaceous additive mixture I;
2) wet mixing lead powder:
The water adding step 1) gained in lead powder mixes swelling agent and carbonaceous additive mixture I, stirs, obtains mixtures II;
3) acid is drenched:
While stirring with shape spray to step 2) add sulfuric acid in gained mixtures II, acid blend II must be drenched;
4) cream is closed:
Step 3) gained is drenched acid blend II rapid stirring even, go out cream and namely obtain start-stop AGM battery terminal negative lead plaster.
Wherein, close in step 4) in cream process and should control to close cream temperature and be less than 65 DEG C, be preferably 40-60 DEG C; Go out cream temperature lower than 45 DEG C, be preferably 20-30 DEG C.
Compared with conventional art, the present invention has following beneficial effect:
1) present invention employs extraordinary mixing carbon adding technique, what greatly improve battery dynamically accepts characteristic, also achieves the raising of battery combination property simultaneously.Meet high magnification charging, electric discharge, long-life demand under start-stop automobile partial state of charge, especially brake energy reclaims function, reduces battery sulfation and improves charging by performance;
2) gained lead plaster of the present invention runs under lower charging voltage for start-stop AGM storage battery, there is excellent charging by performance, cold starting performance and long-life, with reference to Ford standard ES-DS7T-10655-AA, start-stop durability can reach more than 100,000 times, far away higher than common AGM battery and general rich solution maintenance-free lead accumulator;
3) gained lead plaster of the present invention can accept large current charge instantaneously.Test data shows, Performance Detection is carried out according to current international advanced Ford standard (ES-DS7T-10655-AA), adopt the storage battery that cathode lead plaster of the present invention manufactures, its dynamic charging is subject to performance up to 200A, basic mechanical design feature index can reach standard-required, can meet the requirement of user vehicle;
4) technical solution of the present invention technique is simple and easy to control, with low cost, is applicable to suitability for industrialized production.
Embodiment
Following content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; some simple deduction or replace can also be made; all should be considered as belonging to protection scope of the present invention; the present invention uses but the technology be not described and indexing section, is prior art.
Embodiment 1
100kg lead powder (including the PbO of mass fraction 75%) is added and closes in cream machine.High-specific surface area carbon black, 0.3kg low specific surface area conductive carbon black, the ultra-fine barium sulfate of 0.5kg, the sodium lignosulfonate of 0.1kg, the humic acid of 0.5kg in 0.1kg are added water and mix groove, then purifying waste water of 10kg is added, high-speed stirred mixes rear injection and closes cream machine, carry out after wet mixing with lead powder, drenching into density is fast 1.400g/cm
3the sulfuric acid 9kg of (25 DEG C), closes in cream process and controls to close cream temperature at 60 DEG C, stir, be cooled to 40 DEG C, go out cream and namely obtain cathode lead plaster.
Embodiment 2
90kg lead powder (including the PbO of mass fraction 75%) is added and closes in cream machine.High-specific surface area carbon black, 0.2kg low specific surface area conductive carbon black, the ultra-fine barium sulfate of 0.3kg, the sodium lignosulfonate of 0.1kg, the humic acid of 0.1kg in 1kg are added water and mix groove, then purifying waste water of 10kg is added, high-speed stirred mixes rear injection and closes cream machine, carry out after wet mixing with lead powder, drenching into density is fast 1.42g/cm
3the sulfuric acid 3kg of (25 DEG C), closes in cream process and controls to close cream temperature at 60 DEG C, stir, be cooled to 40 DEG C, go out cream and namely obtain cathode lead plaster.
Embodiment 3
100kg lead powder (including the PbO of mass fraction 80%) is added and closes in cream machine.High-specific surface area carbon black, 1kg low specific surface area conductive carbon black, the ultra-fine barium sulfate of 0.5kg, the sodium lignosulfonate of 2kg, the humic acid of 0.2kg in 0.8kg are added water and mix groove, then purifying waste water of 15kg is added, high-speed stirred mixes rear injection and closes cream machine, carry out after wet mixing with lead powder, drenching into density is fast 1.42g/cm
3the sulfuric acid 7kg of (25 DEG C), closes in cream process and controls to close cream temperature at 50 DEG C, stir, be cooled to 30 DEG C, go out cream and namely obtain cathode lead plaster.
Embodiment 4
100kg lead powder (including the PbO of mass fraction 80%) is added and closes in cream machine.High-specific surface area carbon black, 0.2kg low specific surface area conductive carbon black, the ultra-fine barium sulfate of 1kg, the sodium lignosulfonate of 1kg, the humic acid of 0.2kg in 0.1kg are added water and mix groove, then purifying waste water of 15kg is added, high-speed stirred mixes rear injection and closes cream machine, carry out after wet mixing with lead powder, drenching into density is fast 1.45g/cm
3the sulfuric acid 3kg of (25 DEG C), closes in cream process and controls to close cream temperature at 50 DEG C, stir, be cooled to 30 DEG C, go out cream and namely obtain cathode lead plaster.
Embodiment 5
100kg lead powder (including the PbO of mass fraction 85%) is added and closes in cream machine.High-specific surface area carbon black, 0.1kg low specific surface area conductive carbon black, the ultra-fine barium sulfate of 0.2kg, the sodium lignosulfonate of 0.3kg, the humic acid of 0.1kg in 0.5kg are added water and mix groove, then purifying waste water of 9kg is added, high-speed stirred mixes rear injection and closes cream machine, carry out after wet mixing with lead powder, drenching into density is fast 1.45g/cm
3the sulfuric acid 2kg of (25 DEG C), closes in cream process and controls to close cream temperature at 40 DEG C, stir, be cooled to 20 DEG C, go out cream and namely obtain cathode lead plaster.
Checking embodiment
By above-described embodiment 1-5 gained cathode lead plaster, be coated on special grid respectively, through 40 DEG C, 95%RH solidifies 24h, then through 70 DEG C, the dry 24h of 20%RH produces negative raw plate.Just raw plate adopts start-stop AGM anode lead plaster and pole plate manufacture technology to manufacture.
Change into through pole plate, after dry, point plate, the coated AGM dividing plate of pole plate, loads private casing, closes and becomes high-performance AGM battery.
Then gained high-performance AGM battery is carried out performance verification with reference to Ford standard ES-DS7T-10655-AA, and simultaneously with common AGM battery (commercially available prod), and traditional rich solution maintenance-free lead accumulator (disclosed in CN2192080A).The result (for 70Ah battery) is shown in Table 1:
Table 1
As can be seen from table 1 data, the start-stop AGM storage battery adopting novel cathode lead plaster to make and general rich solution maintenance-free lead accumulator have suitable cold-starting ability and good charging performance, dynamically charging is subject to performance then far away higher than common AGM battery and flooded batteries, and obtains the longer start-stop life-span.
Claims (2)
1. a high-performance start-stop AGM negative electrode battery lead plaster, is made up of the material of following weight unit's: lead powder 90-110 part, barium sulfate 0.2-2 part, mixing organic expander 0.1-3 part, mixing carbonaceous additive 0.2-2 part, sulfuric acid 2-10 part and water 9-18 part; Wherein, mixing carbonaceous additive is made up of middle high-specific surface area carbon black 0.1-1 part and low specific surface area conductive carbon black 0.1-1 part, and the middle high-specific surface area carbon black in mixing carbonaceous additive and the mass ratio of low specific surface area conductive carbon black are 1:1-1:3; Middle high-specific surface area carbon black refers to that specific area is 200-2000m
2the carbon black of/g; Low specific surface area conductive carbon black refers to that specific area is less than 100m
2/ g, the carbon black of resistivity≤1.8 Ω m; Mixing organic expander is that the humic acid of 8:1-3:2 and sodium lignosulfonate form by mass ratio.
2. a kind of high-performance start-stop AGM negative electrode battery lead plaster as claimed in claim 1, it is characterized in that, be made up of the material of following weight unit's: 100 parts, lead powder, barium sulfate 0.4-1 part, mixing organic expander 0.4-1 part, mixing carbonaceous additive 0.2-2 part, sulfuric acid 3-7 part and water 10-15 part.
3. a kind of high-performance start-stop AGM negative electrode battery lead plaster as claimed in claim 1, is characterized in that, the PbO containing mass fraction 75-85% in described lead powder.
4. a kind of high-performance start-stop AGM negative electrode battery lead plaster as claimed in claim 1, it is characterized in that, the density of sulfuric acid is 1.2-1.8g/cm
3.
5. the high-performance start-stop AGM battery adopting the cathode lead plaster described in the arbitrary claim of claim 1-4 to make.
6. the preparation method of the high-performance start-stop AGM negative electrode battery lead plaster as described in claim as arbitrary in claim 1-4, step is as follows:
1) water mixes swelling agent and carbonaceous additive:
By mixed expanded dose with mix carbonaceous additive and add water and stir, obtain water and mix swelling agent and carbonaceous additive mixture I;
2) wet mixing lead powder:
The water adding step 1) gained in lead powder mixes swelling agent and carbonaceous additive mixture I, stirs, obtains mixtures II;
3) acid is drenched:
While stirring with shape spray to step 2) add sulfuric acid in gained mixtures II, acid blend II must be drenched;
4) cream is closed:
Step 3) gained is drenched acid blend II rapid stirring even, go out cream and namely obtain start-stop AGM battery terminal negative lead plaster.
7. the preparation method of high-performance start-stop AGM negative electrode battery lead plaster as claimed in claim 6, is characterized in that, closing in step 4) in cream process and should controlling conjunction cream temperature is 40-60 DEG C.
8. the preparation method of high-performance start-stop AGM negative electrode battery lead plaster as claimed in claim 7, it is characterized in that, going out cream temperature is 20-30 DEG C.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107820643B (en) * | 2015-06-24 | 2021-07-20 | 卡博特公司 | Carbonaceous materials for lead-acid batteries |
| CN105609781B (en) * | 2015-12-23 | 2018-08-24 | 天能电池集团有限公司 | A kind of acid accumulator negative pole lead compound organic expander and preparation method thereof |
| CN111525195B (en) * | 2019-02-01 | 2022-04-26 | 骆驼集团蓄电池研究院有限公司 | Maintenance-free lead-acid storage battery with excellent deep cycle life and production method thereof |
| CN111326713A (en) * | 2020-02-19 | 2020-06-23 | 浙江埃登达新能源材料有限公司 | Power battery cathode material and preparation method thereof |
| CN114759170A (en) * | 2021-05-07 | 2022-07-15 | 广州倬粤电能科技有限公司 | Preparation method of graphene quantum dot composite material for lead-acid battery |
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