WO2022095158A1 - Power lead storage battery formation, screening and matching process - Google Patents
Power lead storage battery formation, screening and matching process Download PDFInfo
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- WO2022095158A1 WO2022095158A1 PCT/CN2020/131750 CN2020131750W WO2022095158A1 WO 2022095158 A1 WO2022095158 A1 WO 2022095158A1 CN 2020131750 W CN2020131750 W CN 2020131750W WO 2022095158 A1 WO2022095158 A1 WO 2022095158A1
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- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 89
- 238000012216 screening Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 42
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 230000010287 polarization Effects 0.000 claims abstract description 7
- 230000002159 abnormal effect Effects 0.000 claims description 35
- 208000028659 discharge Diseases 0.000 claims description 35
- 238000001931 thermography Methods 0.000 claims description 6
- 230000035515 penetration Effects 0.000 claims description 5
- 230000007423 decrease Effects 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 18
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000002950 deficient Effects 0.000 abstract description 5
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 238000007599 discharging Methods 0.000 abstract description 3
- 239000002344 surface layer Substances 0.000 abstract description 3
- 238000003487 electrochemical reaction Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000012466 permeate Substances 0.000 abstract 3
- 239000013543 active substance Substances 0.000 abstract 1
- 238000011056 performance test Methods 0.000 description 6
- 238000007689 inspection Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 238000012790 confirmation Methods 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
- H01M10/446—Initial charging measures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
- B07C—POSTAL SORTING; SORTING INDIVIDUAL ARTICLES, OR BULK MATERIAL FIT TO BE SORTED PIECE-MEAL, e.g. BY PICKING
- B07C5/00—Sorting according to a characteristic or feature of the articles or material being sorted, e.g. by control effected by devices which detect or measure such characteristic or feature; Sorting by manually actuated devices, e.g. switches
- B07C5/34—Sorting according to other particular properties
- B07C5/344—Sorting according to other particular properties according to electric or electromagnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
- B07C—POSTAL SORTING; SORTING INDIVIDUAL ARTICLES, OR BULK MATERIAL FIT TO BE SORTED PIECE-MEAL, e.g. BY PICKING
- B07C5/00—Sorting according to a characteristic or feature of the articles or material being sorted, e.g. by control effected by devices which detect or measure such characteristic or feature; Sorting by manually actuated devices, e.g. switches
- B07C5/36—Sorting apparatus characterised by the means used for distribution
- B07C5/361—Processing or control devices therefor, e.g. escort memory
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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
- H01M10/04—Construction or manufacture in general
- H01M10/0404—Machines for assembling batteries
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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
- H01M10/12—Construction or manufacture
-
- 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
Definitions
- the invention relates to the field of storage batteries, in particular to a process for forming, screening and matching of power lead storage batteries.
- Electric vehicles are well received by consumers in the domestic market due to their advantages of lightness, convenience and low price.
- Lead-acid batteries have been widely promoted in electric vehicles in recent years due to their high cost performance, good power characteristics, small self-discharge, and low price.
- the charging and forming process of the battery manufacturing process the total charging and discharging time is about 67h
- the first stage forming time is about 39h
- the second stage capacity inspection and charging and floating charging stage are about 18h, accounting for the entire charging and discharging time process. 1/4 of the time.
- Capacitance test and discharge to 10.5V the purpose is to match batteries of similar capacity, and to pick out low-voltage abnormal batteries.
- the present invention provides a power lead-acid battery formation, screening and matching process, which optimizes the difficulty of electrolyte penetration, uneven formation of polar plates, and inconsistent PbO 2 content in the formation stage, and shortens the time.
- the capacity inspection and the time of the charging float phase improve the production efficiency.
- the present invention provides a power lead-acid battery formation, screening and matching process, which is characterized in that it includes a formation stage and a screening and matching stage, and the formation stage includes:
- Discharge after surface formation discharge at 0.3-0.5C for 0.5-1.5h to eliminate the polarization voltage and at the same time make the acid penetration uniform;
- Discharge after the formation of the middle layer discharge at a current of 1.9-2.1C for 9-11min to make the acid liquid penetrate evenly;
- the screening and matching stage includes:
- High current discharge discharge at 0.4-0.6C current for 20-40min, and assign groups according to the voltage value;
- the formation depth is 28-32% of the total thickness of the grid; in the middle formation stage, the formation thickness is 60-70% of the total grid thickness %; in the formation stage of the outermost layer, the formation thickness is 100% of the total thickness of the grid.
- an abnormal battery whose voltage value is lower than 15.5V is marked once.
- the secondary mark passes through the abnormal battery whose voltage shows a steep slope drop in the abnormal battery of the primary mark. Judging from the voltage curve, if the voltage drops steeply, it will be marked twice.
- abnormal batteries with internal short-circuit voltage lower than 15.5v and large battery heat generation among abnormal batteries that have passed the secondary marking three times are marked, and defective batteries that have been marked three times are selected.
- the abnormal battery whose internal short-circuit voltage does not rise and the battery generates a large amount of heat is determined by means of infrared thermal imaging.
- the present invention adopts the above-mentioned power lead-acid battery formation, screening and matching process, and is suitable for power battery series.
- the first stage is the formation stage, and different high currents are used to carry out the surface formation stage, the middle layer formation stage, and the outermost formation stage.
- the electrochemical reaction takes place fully.
- Make the positive plate generate more lead dioxide and the negative electrode to generate more metal spongy lead.
- the first step of standing is added to make the acid solution infiltrate uniformly.
- high current discharge is used to eliminate the polarization voltage, reduce the internal resistance, make the acid solution penetrate evenly again, and make the internal active material of the battery better conversion reaction .
- the second stage is the screening and matching stage, monitoring the triple screening of low voltage, fast voltage drop, and battery heating, and finally picking out bad batteries.
- the total formation time of this process is about 57h, the production efficiency is increased by about 10%, and the charging rate is 7-8 times, which meets the requirements of formation performance.
- the difficulty of electrolyte penetration, uneven formation of polar plates, and inconsistent PbO 2 content in the formation stage are optimized, the time for capacity inspection and charging and floating stages is shortened, and production efficiency is improved.
- Figure 1 is a schematic diagram of the grid formation sequence
- Figure 2 is a picture of infrared thermal imaging of the internal heat generation of an abnormal battery.
- Embodiment 1 is a diagrammatic representation of Embodiment 1:
- the first stage the transformation stage
- Discharge after surface formation discharge at 40A for 1h to eliminate the polarization voltage, and at the same time make the acid solution penetrate evenly
- the second stage screening and matching stage
- Small current floating charge charge at 4A for 4h, monitor whether the voltage value is between 15.5-15.8V; mark the abnormal battery whose voltage value is below 15.8V;
- High-current discharge discharge at 50A for 30min, and assign groups according to the voltage value. At the same time, monitor whether the voltage of the abnormal battery that has been marked once drops too fast, and if the voltage drops too fast (for example, according to the voltage curve, if the voltage drops steeply, It is the abnormal battery that falls too fast) for secondary marking confirmation.
- Supplementary power charge at 20A for 30min, and through infrared thermal imaging, the internal short-circuit voltage of the abnormal battery that has been marked twice is lower than 15.5v and the battery generates a large amount of heat (see Figure 2, the temperature of the single cell on the right side of the picture is 26.6 °C is significantly higher than other cells, the battery is abnormal, and the abnormal battery is selected for three times to confirm the abnormal battery, and finally the defective battery that has been marked three times is selected.
- the performance test meets the requirements of the national standard, and the cycle life is improved compared with the conventional process.
- Embodiment 2 is a diagrammatic representation of Embodiment 1:
- the first stage the transformation stage
- the second stage screening and matching stage
- High-current discharge Discharge at 51A for 30 minutes, and assign groups according to the voltage value. At the same time, monitor whether the voltage of the abnormal battery that has been marked once drops too fast, and if the voltage drops too fast (for example, according to the voltage curve, if the voltage drops steeply, It is the abnormal battery that falls too fast) for secondary marking confirmation.
- Supplementary power charge at 21A for 30 minutes, and through infrared thermal imaging, the internal short-circuit voltage of the abnormal battery that has been marked twice is lower than 15.5v and the battery generates a large amount of heat (see Figure 2, the temperature of the single cell on the right side of the picture is 26.6 °C is significantly higher than other cells, the battery is abnormal, and the abnormal battery is selected for three times to confirm the abnormal battery, and finally the defective battery that has been marked three times is selected.
- the performance test meets the requirements of the national standard, and the cycle life is improved compared with the conventional process.
- Embodiment 3 is a diagrammatic representation of Embodiment 3
- the first stage the transformation stage
- the second stage screening and matching stage
- High-current discharge Discharge at 53A for 30 minutes, and assign groups according to the voltage value. At the same time, monitor whether the voltage of the abnormal battery that has been marked once drops too fast, and if the voltage drops too fast (for example, according to the voltage curve, if the voltage drops steeply, It is the abnormal battery that falls too fast) for secondary marking confirmation.
- Supplementary power charge at 20A for 30min, and through infrared thermal imaging, the internal short-circuit voltage of the abnormal battery that has been marked twice is lower than 15.5v and the battery generates a large amount of heat (see Figure 2, the temperature of the single cell on the right side of the picture is 26.6 °C is significantly higher than other cells, the battery is abnormal, and the abnormal battery is selected for three times to confirm the abnormal battery, and finally the defective battery that has been marked three times is selected.
- the performance test meets the requirements of the national standard, and the cycle life is improved compared with the conventional process.
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
A power lead storage battery formation, screening and matching process, relating to the field of power batteries. At a formation phase, different large currents are used to implement a surface layer formation phase, a middle layer formation phase, and an outermost layer formation phase, and sufficient electrochemical reaction is enabled. A positive electrode plate generates more lead dioxide, and a negative electrode generates more metallic spongy lead. In addition, an initial step of standing is added to make an acid liquid permeate uniformly; after the surface layer and middle layer formation phases, large currents are separately used for discharging, so as to eliminate a polarization voltage, reduce the internal resistance, make the acid liquid permeate uniformly again, and make active substances inside a battery better converted and reacted. At a screening and matching phase, a low voltage, a fast voltage drop, and battery heating are detected to achieve triple screening, so as to finally pick out defective batteries. The situation where at a formation phase, it is difficult for an electrolyte to permeate, electrode plate formation is not uniform, and the content of PbO2 is inconsistent is improved; the total formation time is about 57 h; the production efficiency is improved by about 10%; the charging rate is 7-8 times; the formation performance requirement is satisfied.
Description
本发明涉及蓄电池领域，特别涉及一种动力铅蓄电池化成、筛选配组工艺。The invention relates to the field of storage batteries, in particular to a process for forming, screening and matching of power lead storage batteries.
电动汽车以其轻捷、方便、价格低廉等优势，在国内市场深受广大消费者的欢迎。铅蓄电池因性价比高、功率特性好，自放电小，价格便宜，近年来在电动汽车中得到了全面推广。目前，蓄电池的制造过程充电化成工序，充放电化成总时间在67h左右，第一阶段化成时间为39h左右，其第二阶段容检以及充电浮充阶段18h左右，占整个充放电化成时间过程的1/4的时间。容检放电到10.5V，目的为了相近容量的电池配组，以及挑出低电压异常电池。Electric vehicles are well received by consumers in the domestic market due to their advantages of lightness, convenience and low price. Lead-acid batteries have been widely promoted in electric vehicles in recent years due to their high cost performance, good power characteristics, small self-discharge, and low price. At present, the charging and forming process of the battery manufacturing process, the total charging and discharging time is about 67h, the first stage forming time is about 39h, and the second stage capacity inspection and charging and floating charging stage are about 18h, accounting for the entire charging and discharging time process. 1/4 of the time. Capacitance test and discharge to 10.5V, the purpose is to match batteries of similar capacity, and to pick out low-voltage abnormal batteries.
通常情况下，在化成工序中会出现电解液渗透困难、极板化成不均匀、PbO
2含量不一致的技术问题，在容检以及充电浮充阶段时间较长，生产效率低下。
Under normal circumstances, in the formation process, there will be technical problems such as difficulty in penetration of electrolyte, uneven formation of polar plates, and inconsistent PbO 2 content. It takes a long time in the capacity inspection and charging and floating stages, and the production efficiency is low.
发明内容SUMMARY OF THE INVENTION
发明目的：针对现有技术中存在的问题，本发明提供一种动力铅蓄电池化成、筛选配组工艺，优化了化成阶段电解液渗透困难、极板化成不均匀、PbO
2含量不一致情况，缩短了容检以及充电浮充阶段的时间，提高了生产效率。
Purpose of the invention: Aiming at the problems existing in the prior art, the present invention provides a power lead-acid battery formation, screening and matching process, which optimizes the difficulty of electrolyte penetration, uneven formation of polar plates, and inconsistent PbO 2 content in the formation stage, and shortens the time. The capacity inspection and the time of the charging float phase improve the production efficiency.
技术方案：本发明提供了一种动力铅蓄电池化成、筛选配组工艺，其特征在于，包括化成阶段和筛选配组阶段，所述化成阶段包括：Technical solution: The present invention provides a power lead-acid battery formation, screening and matching process, which is characterized in that it includes a formation stage and a screening and matching stage, and the formation stage includes:
化成静置：电池加酸后静置0.5-1.5h，使酸液渗透均匀；Formation and standing: the battery is left to stand for 0.5-1.5h after adding acid, so that the acid solution penetrates evenly;
表层化成superficial
充电：以1.6-2.0C电流充电9-11h；Charging: Charge with 1.6-2.0C current for 9-11h;
充电：以1.4-1.8C电流充电15-17h；Charging: Charge with 1.4-1.8C current for 15-17h;
表层化成后放电：以0.3-0.5C电流放电0.5-1.5h，消除极化电压，同时使酸液渗透均匀；Discharge after surface formation: discharge at 0.3-0.5C for 0.5-1.5h to eliminate the polarization voltage and at the same time make the acid penetration uniform;
中层化成Middle layer formation
充电：以1.8-2.0C电流充电1.5-2.5h；Charging: Charge with 1.8-2.0C current for 1.5-2.5h;
充电：以1.6-1.8C电流充电9-11h；Charging: Charge with 1.6-1.8C current for 9-11h;
中层化成后放电：以1.9-2.1C电流放电9-11min，使酸液渗透均匀；Discharge after the formation of the middle layer: discharge at a current of 1.9-2.1C for 9-11min to make the acid liquid penetrate evenly;
最外层化成outermost layer
充电：以1.4-1.6C电流充电7-9h；Charging: charging with 1.4-1.6C current for 7-9h;
充电：以0.03-0.05C电流充电3-5h，浮充电压15.7-16V以上抽酸；Charging: charge at 0.03-0.05C current for 3-5h, and pump acid at a float voltage of 15.7-16V or more;
所述筛选配组阶段包括：The screening and matching stage includes:
筛选配组静置：静置5-15min；Screening and group standing: standing for 5-15min;
小电流浮充：以0.03-0.05C电流充电3-5h，监测电压值15.5-15.8V；Small current floating charge: charge at 0.03-0.05C current for 3-5h, monitor voltage value 15.5-15.8V;
大电流放电：以0.4-0.6C电流放电20-40min，根据电压值分档配组；High current discharge: discharge at 0.4-0.6C current for 20-40min, and assign groups according to the voltage value;
补充电：以1.9-2.1C电流充电20-40min。Supplementary power: charge at 1.9-2.1C current for 20-40min.
优选地，以板栅筋条表面为基准，在所述表层化成阶段，化成深度为板栅总厚度的28～32％；在所述中层化成阶段，化成厚度为板栅总厚度的60～70％；在所述最外层化成阶段，化成厚度为板栅总厚度的100％。Preferably, taking the grid rib surface as the benchmark, in the surface formation stage, the formation depth is 28-32% of the total thickness of the grid; in the middle formation stage, the formation thickness is 60-70% of the total grid thickness %; in the formation stage of the outermost layer, the formation thickness is 100% of the total thickness of the grid.
优选地，在所述小电流浮充阶段，一次标记电压值低于15.5V的异常电池。Preferably, in the small current floating charge stage, an abnormal battery whose voltage value is lower than 15.5V is marked once.
优选地，在所述大电流放电阶段，二次标记经过所述一次标记的异常电池中电压呈陡坡式下降的异常电池。根据电压曲线判断，若电压呈陡坡式下降，则对其进行二次标记。Preferably, in the high-current discharge stage, the secondary mark passes through the abnormal battery whose voltage shows a steep slope drop in the abnormal battery of the primary mark. Judging from the voltage curve, if the voltage drops steeply, it will be marked twice.
优选地，在所述补充电阶段，三次标记经过所述二次标记的异常电池中内部短路电压低于15.5v且电池发热量较大的异常电池，并挑出经过三次标记的不良电池。Preferably, in the supplementary charging stage, abnormal batteries with internal short-circuit voltage lower than 15.5v and large battery heat generation among abnormal batteries that have passed the secondary marking three times are marked, and defective batteries that have been marked three times are selected.
优选地，通过红外线热成像的方法判断所述内部短路电压上不来且电池发热量较大的异常电池。Preferably, the abnormal battery whose internal short-circuit voltage does not rise and the battery generates a large amount of heat is determined by means of infrared thermal imaging.
有益效果：本发明采用上述动力铅蓄电池化成、筛选配组工艺，适用于动力电池系列，第一阶段为化成阶段，采用不同大电流进行表层化成阶段、中层化成阶段、最外层化成阶段，进行充分发生电化学反应。使正极板生成更多的二氧化铅，负极生成更多的金属海绵状铅。同时增加首步静置使酸液渗透均匀，表层化成和中层化成阶段后分别采用大电流放电，消除极化电压，降低内阻，使酸液再次渗透均匀，使电池内部活性物质更好转化反应。第二阶段为筛选配组阶段，监测低电压、压降快、电池发热三重筛选，最终挑出不良电池。本工艺总化成时间为57h左右，生产效率提升10％左右，充电倍率7-8倍，满足化成性能要求。优化了化成阶段电解液渗透困难、极板化成不均匀、PbO
2含量不一致情况，缩短了容检以及充电浮充阶段的时间，提高了生产效率。
Beneficial effects: The present invention adopts the above-mentioned power lead-acid battery formation, screening and matching process, and is suitable for power battery series. The first stage is the formation stage, and different high currents are used to carry out the surface formation stage, the middle layer formation stage, and the outermost formation stage. The electrochemical reaction takes place fully. Make the positive plate generate more lead dioxide and the negative electrode to generate more metal spongy lead. At the same time, the first step of standing is added to make the acid solution infiltrate uniformly. After the surface layer formation and the middle layer formation stage, high current discharge is used to eliminate the polarization voltage, reduce the internal resistance, make the acid solution penetrate evenly again, and make the internal active material of the battery better conversion reaction . The second stage is the screening and matching stage, monitoring the triple screening of low voltage, fast voltage drop, and battery heating, and finally picking out bad batteries. The total formation time of this process is about 57h, the production efficiency is increased by about 10%, and the charging rate is 7-8 times, which meets the requirements of formation performance. The difficulty of electrolyte penetration, uneven formation of polar plates, and inconsistent PbO 2 content in the formation stage are optimized, the time for capacity inspection and charging and floating stages is shortened, and production efficiency is improved.
图1为板栅化成顺序示意图；Figure 1 is a schematic diagram of the grid formation sequence;
图2为对异常电池的内部发热量进行红外线热成像的图片。Figure 2 is a picture of infrared thermal imaging of the internal heat generation of an abnormal battery.
下面结合附图对本发明进行详细的介绍。The present invention will be described in detail below with reference to the accompanying drawings.
实施方式1：Embodiment 1:
以12V100Ah动力铅蓄电池为例，化成、筛选配组工艺如下Taking 12V100Ah power lead-acid battery as an example, the formation, screening and grouping process is as follows
第一阶段：化成阶段The first stage: the transformation stage
化成静置：电池加酸静置1h，使液渗透均匀；Formation and standing: The battery is added with acid and allowed to stand for 1 hour to make the liquid penetrate evenly;
表层化成(以板栅筋条表面为基准，此阶段化成深度为板栅总厚度的30％，见图1)Surface formation (based on the grid rib surface, the formation depth at this stage is 30% of the total thickness of the grid, see Figure 1)
充电：以18A充电10hCharging: 10h at 18A
充电：以16A充电16hCharging: 16h at 16A
表层化成后放电：以40A放电1h，消除极化电压，同时使酸液渗透均匀Discharge after surface formation: discharge at 40A for 1h to eliminate the polarization voltage, and at the same time make the acid solution penetrate evenly
中层化成(以板栅筋条表面为基准，此阶段化成深度为板栅总厚度的60％，见图1)Formation of the middle layer (based on the surface of the grid rib, the formation depth at this stage is 60% of the total thickness of the grid, see Figure 1)
充电：以19A充电2hCharging: 2h at 19A
充电：以17A充电10hCharging: 10h at 17A
中层化成后放电：以20A放电10min，使酸液渗透均匀Discharge after the formation of the middle layer: discharge at 20A for 10min to make the acid liquid penetrate evenly
最外层化成(以板栅筋条表面为基准，此阶段化成深度为板栅总厚度的100％，见图1)Formation of the outermost layer (based on the surface of the grid rib, the formation depth at this stage is 100% of the total thickness of the grid, see Figure 1)
充电：以15A充电8hCharging: 8h at 15A
充电：以4A充电4h，浮充电压16V以上抽酸Charging: charge at 4A for 4h, and pump acid with a float voltage above 16V
第二阶段：筛选配组阶段The second stage: screening and matching stage
筛选配组静置：10min；Screening and group standing: 10min;
小电流浮充：以4A充电4h，监测电压值是否在15.5-15.8V之间；对监测到电压值在15.8V以下的异常电池做一次标记；Small current floating charge: charge at 4A for 4h, monitor whether the voltage value is between 15.5-15.8V; mark the abnormal battery whose voltage value is below 15.8V;
大电流放电：以50A放电30min，根据电压值分档配组，同时监测经过一次标记的异常电池的电压是否下降太快，对下降太快(如根据电压曲线判断，若电压呈陡坡式下降，则是下降太快)的异常电池进行二次标记确认。High-current discharge: discharge at 50A for 30min, and assign groups according to the voltage value. At the same time, monitor whether the voltage of the abnormal battery that has been marked once drops too fast, and if the voltage drops too fast (for example, according to the voltage curve, if the voltage drops steeply, It is the abnormal battery that falls too fast) for secondary marking confirmation.
补充电：以20A充电30min，通过红外线热成像的方法，对经过二次标记的异常电池中内部短路电压低于15.5v且电池发热量较大(见图2，图片的右侧单格温度26.6℃明显高于其他单格，电池存在异常，挑出不良电池)的异常电池进行三次标记确认，最终挑出经过三次标记的不良电池。Supplementary power: charge at 20A for 30min, and through infrared thermal imaging, the internal short-circuit voltage of the abnormal battery that has been marked twice is lower than 15.5v and the battery generates a large amount of heat (see Figure 2, the temperature of the single cell on the right side of the picture is 26.6 ℃ is significantly higher than other cells, the battery is abnormal, and the abnormal battery is selected for three times to confirm the abnormal battery, and finally the defective battery that has been marked three times is selected.
随机挑出5只12V100Ah动力铅蓄电池进行成组性能检测，见下表1Randomly select 5 12V100Ah power lead-acid batteries for group performance testing, see Table 1 below
表1：12V100Ah成组性能检测结果Table 1: 12V100Ah group performance test results
性能检测符合国标要求，与常规工艺对比循环寿命有所提升。The performance test meets the requirements of the national standard, and the cycle life is improved compared with the conventional process.
实施方式2：Embodiment 2:
以12V100Ah动力铅蓄电池为例，化成、筛选配组工艺如下Taking 12V100Ah power lead-acid battery as an example, the formation, screening and grouping process is as follows
第一阶段：化成阶段The first stage: the transformation stage
化成静置：电池加酸静置1h，使液渗透均匀；Formation and standing: The battery is added with acid and allowed to stand for 1 hour to make the liquid penetrate evenly;
表层化成(以板栅筋条表面为基准，此阶段化成深度为板栅总厚度的30％，见图1)Surface formation (based on the grid rib surface, the formation depth at this stage is 30% of the total thickness of the grid, see Figure 1)
充电：以17A充电10hCharging: 10h at 17A
充电：以15A充电16hCharging: 16h at 15A
表层化成后放电：以39A放电1h，消除极化电压，同时使酸液渗透均匀Discharge after surface formation: discharge at 39A for 1h to eliminate the polarization voltage and at the same time make the acid solution penetrate evenly
中层化成(以板栅筋条表面为基准，此阶段化成深度为板栅总厚度的60％，见图1)Formation of the middle layer (based on the surface of the grid rib, the formation depth at this stage is 60% of the total thickness of the grid, see Figure 1)
充电：以18A充电2hCharging: 2h at 18A
充电：以16A充电10hCharging: 10h at 16A
中层化成后放电：以20A放电10min，使酸液渗透均匀Discharge after the formation of the middle layer: discharge at 20A for 10min to make the acid liquid penetrate evenly
最外层化成(以板栅筋条表面为基准，此阶段化成深度为板栅总厚度的100％，见图1)Formation of the outermost layer (based on the surface of the grid rib, the formation depth at this stage is 100% of the total thickness of the grid, see Figure 1)
充电：以15.2A充电8hCharging: 8h at 15.2A
充电：以4.4A充电4h，浮充电压16V以上抽酸Charging: charge at 4.4A for 4h, and pump acid with a float voltage above 16V
第二阶段：筛选配组阶段The second stage: screening and matching stage
筛选配组静置：10min；Screening and group standing: 10min;
小电流浮充：以4.1A充电4h，监测电压值是否在15.5-15.8V之间；对监测到电压值在15.8V以下的异常电池做一次标记；Small current floating charge: charge at 4.1A for 4h, monitor whether the voltage value is between 15.5-15.8V; mark the abnormal battery whose voltage value is below 15.8V;
大电流放电：以51A放电30min，根据电压值分档配组，同时监测经过一次标记的异常电池的电压是否下降太快，对下降太快(如根据电压曲线判断，若电压呈陡坡式下降，则是下降太快)的异常电池进行二次标记确认。High-current discharge: Discharge at 51A for 30 minutes, and assign groups according to the voltage value. At the same time, monitor whether the voltage of the abnormal battery that has been marked once drops too fast, and if the voltage drops too fast (for example, according to the voltage curve, if the voltage drops steeply, It is the abnormal battery that falls too fast) for secondary marking confirmation.
补充电：以21A充电30min，通过红外线热成像的方法，对经过二次标记的异常电池中内部短路电压低于15.5v且电池发热量较大(见图2，图片的右侧单格温度26.6℃明显高于其 他单格，电池存在异常，挑出不良电池)的异常电池进行三次标记确认，最终挑出经过三次标记的不良电池。Supplementary power: charge at 21A for 30 minutes, and through infrared thermal imaging, the internal short-circuit voltage of the abnormal battery that has been marked twice is lower than 15.5v and the battery generates a large amount of heat (see Figure 2, the temperature of the single cell on the right side of the picture is 26.6 ℃ is significantly higher than other cells, the battery is abnormal, and the abnormal battery is selected for three times to confirm the abnormal battery, and finally the defective battery that has been marked three times is selected.
随机挑出5只12V100Ah动力铅蓄电池进行成组性能检测，见下表21Randomly select 5 12V100Ah power lead-acid batteries for group performance testing, see Table 21 below
表2：12V100Ah成组性能检测结果Table 2: 12V100Ah group performance test results
性能检测符合国标要求，与常规工艺对比循环寿命有所提升。The performance test meets the requirements of the national standard, and the cycle life is improved compared with the conventional process.
实施方式3：Embodiment 3:
以12V100Ah动力铅蓄电池为例，化成、筛选配组工艺如下Taking 12V100Ah power lead-acid battery as an example, the formation, screening and grouping process is as follows
第一阶段：化成阶段The first stage: the transformation stage
化成静置：电池加酸静置1h，使液渗透均匀；Formation and standing: The battery is added with acid and allowed to stand for 1 hour to make the liquid penetrate evenly;
表层化成(以板栅筋条表面为基准，此阶段化成深度为板栅总厚度的30％，见图1)Surface formation (based on the grid rib surface, the formation depth at this stage is 30% of the total thickness of the grid, see Figure 1)
充电：以17.5A充电10hCharging: 10h at 17.5A
充电：以15.8A充电16hCharging: 16h at 15.8A
表层化成后放电：以41A放电1h，消除极化电压，同时使酸液渗透均匀Discharge after surface formation: discharge at 41A for 1h to eliminate the polarization voltage and at the same time make the acid solution penetrate evenly
中层化成(以板栅筋条表面为基准，此阶段化成深度为板栅总厚度的60％，见图1)Formation of the middle layer (based on the surface of the grid rib, the formation depth at this stage is 60% of the total thickness of the grid, see Figure 1)
充电：以18.5A充电2hCharging: 2h at 18.5A
充电：以16.9A充电10hCharging: 10h at 16.9A
中层化成后放电：以20A放电10min，使酸液渗透均匀Discharge after the formation of the middle layer: discharge at 20A for 10min to make the acid liquid penetrate evenly
最外层化成(以板栅筋条表面为基准，此阶段化成深度为板栅总厚度的100％，见图1)Formation of the outermost layer (based on the surface of the grid rib, the formation depth at this stage is 100% of the total thickness of the grid, see Figure 1)
充电：以15.3A充电8hCharging: 8h at 15.3A
充电：以4.2A充电4h，浮充电压16V以上抽酸Charging: charge at 4.2A for 4h, and pump acid with a float voltage above 16V
第二阶段：筛选配组阶段The second stage: screening and matching stage
筛选配组静置：10min；Screening and group standing: 10min;
小电流浮充：以4.2A充电4h，监测电压值是否在15.5-15.8V之间；对监测到电压值在15.8V以下的异常电池做一次标记；Small current floating charge: charge at 4.2A for 4h, monitor whether the voltage value is between 15.5-15.8V; mark the abnormal battery whose voltage value is below 15.8V;
大电流放电：以53A放电30min，根据电压值分档配组，同时监测经过一次标记的异常电池的电压是否下降太快，对下降太快(如根据电压曲线判断，若电压呈陡坡式下降，则是下降太快)的异常电池进行二次标记确认。High-current discharge: Discharge at 53A for 30 minutes, and assign groups according to the voltage value. At the same time, monitor whether the voltage of the abnormal battery that has been marked once drops too fast, and if the voltage drops too fast (for example, according to the voltage curve, if the voltage drops steeply, It is the abnormal battery that falls too fast) for secondary marking confirmation.
补充电：以20A充电30min，通过红外线热成像的方法，对经过二次标记的异常电池中内部短路电压低于15.5v且电池发热量较大(见图2，图片的右侧单格温度26.6℃明显高于其他单格，电池存在异常，挑出不良电池)的异常电池进行三次标记确认，最终挑出经过三次标记的不良电池。Supplementary power: charge at 20A for 30min, and through infrared thermal imaging, the internal short-circuit voltage of the abnormal battery that has been marked twice is lower than 15.5v and the battery generates a large amount of heat (see Figure 2, the temperature of the single cell on the right side of the picture is 26.6 ℃ is significantly higher than other cells, the battery is abnormal, and the abnormal battery is selected for three times to confirm the abnormal battery, and finally the defective battery that has been marked three times is selected.
随机挑出5只12V100Ah动力铅蓄电池进行成组性能检测，见下表2Randomly select 5 12V100Ah power lead-acid batteries for group performance testing, see Table 2 below
表3：12V100Ah成组性能检测结果Table 3: 12V100Ah group performance test results
性能检测符合国标要求，与常规工艺对比循环寿命有所提升。The performance test meets the requirements of the national standard, and the cycle life is improved compared with the conventional process.
上述实施方式只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所做的等效变换或修饰，都应涵盖在本发明的保护范围之内。The above-mentioned embodiments are only intended to illustrate the technical concept and characteristics of the present invention, and the purpose is to enable those who are familiar with the art to understand the content of the present invention and implement it accordingly, and cannot limit the protection scope of the present invention. All equivalent transformations or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (6)
- 一种动力铅蓄电池化成、筛选配组工艺，其特征在于，包括化成阶段和筛选配组阶段，所述化成阶段包括：A power lead-acid battery formation, screening and matching process, characterized in that it includes a formation stage and a screening and matching stage, and the formation stage includes:化成静置：电池加酸后静置0.5-1.5h，使酸液渗透均匀；Formation and standing: the battery is left to stand for 0.5-1.5h after adding acid, so that the acid solution penetrates evenly;表层化成superficial充电：以1.6-2.0C电流充电9-11h；Charging: Charge with 1.6-2.0C current for 9-11h;充电：以1.4-1.8C电流充电15-17h；Charging: Charge with 1.4-1.8C current for 15-17h;表层化成后放电：以0.3-0.5C电流放电0.5-1.5h，消除极化电压，同时使酸液渗透均匀；Discharge after surface formation: discharge at 0.3-0.5C for 0.5-1.5h to eliminate the polarization voltage and at the same time make the acid penetration uniform;中层化成Middle layer formation充电：以1.8-2.0C电流充电1.5-2.5h；Charging: Charge with 1.8-2.0C current for 1.5-2.5h;充电：以1.6-1.8C电流充电9-11h；Charging: Charge with 1.6-1.8C current for 9-11h;中层化成后放电：以1.9-2.1C电流放电9-11min，使酸液渗透均匀；Discharge after the formation of the middle layer: discharge at a current of 1.9-2.1C for 9-11min to make the acid liquid penetrate evenly;最外层化成outermost layer充电：以1.4-1.6C电流充电7-9h；Charging: charge at 1.4-1.6C current for 7-9h;充电：以0.03-0.05C电流充电3-5h，浮充电压15.7-16V以上抽酸；Charging: charge at 0.03-0.05C current for 3-5h, and pump acid at a float voltage of 15.7-16V or more;所述筛选配组阶段包括：The screening and matching stage includes:筛选配组静置：静置5-15min；Screening and group standing: standing for 5-15min;小电流浮充：以0.03-0.05C电流充电3-5h，监测电压值是否在15.5-15.8V之间；Small current floating charge: charge with 0.03-0.05C current for 3-5h, and monitor whether the voltage value is between 15.5-15.8V;大电流放电：以0.4-0.6C电流放电20-40min，根据电压值分档配组；High current discharge: discharge at 0.4-0.6C current for 20-40min, and assign groups according to the voltage value;补充电：以1.9-2.1C电流充电20-40min。Supplementary power: charge at 1.9-2.1C current for 20-40min.
- 根据权利要求1所述的动力铅蓄电池化成、筛选配组工艺，其特征在于，以板栅筋条表面为基准，在所述表层化成阶段，化成深度为板栅总厚度的28～32％；在所述中层化成阶段，化成厚度为板栅总厚度的60～70％；在所述最外层化成阶段，化成厚度为板栅总厚度的100％。The power lead-acid battery formation, screening and grouping process according to claim 1, characterized in that, taking the grid rib surface as a benchmark, in the surface formation stage, the formation depth is 28-32% of the total thickness of the grid; In the formation stage of the middle layer, the formation thickness is 60-70% of the total thickness of the grid; in the formation stage of the outermost layer, the formation thickness is 100% of the total thickness of the grid.
- 根据权利要求1所述的动力铅蓄电池化成、筛选配组工艺，其特征在于，在所述小电流浮充阶段，一次标记电压值低于15.5V的异常电池。The power lead-acid battery formation, screening and grouping process according to claim 1, characterized in that, in the low-current float charging stage, an abnormal battery whose voltage value is lower than 15.5V is marked once.
- 根据权利要求3所述的动力铅蓄电池化成、筛选配组工艺，其特征在于，在所述大电流放电阶段，二次标记经过所述一次标记的异常电池中电压呈 陡坡式下降的异常电池。The power lead-acid battery formation, screening and grouping process according to claim 3, characterized in that, in the high-current discharge stage, the secondary marking passes through the abnormal battery whose voltage shows a steep slope decline in the abnormal battery of the primary marking.
- 根据权利要求4所述的动力铅蓄电池化成、筛选配组工艺，其特征在于，在所述补充电阶段，三次标记经过所述二次标记的异常电池中内部短路电压低于15.5v且电池发热量较大的异常电池，并挑出经过三次标记的不良电池。The power lead-acid battery formation, screening and matching process according to claim 4, characterized in that, in the supplementary charging stage, the internal short-circuit voltage of the abnormal battery marked three times after the secondary marking is lower than 15.5v and the battery has Abnormal batteries with high heat, and pick out bad batteries that have been marked three times.
- 根据权利要求5所述的动力铅蓄电池化成、筛选配组工艺，其特征在于，通过红外线热成像的方法判断所述内部短路电压上不来且电池发热量较大的异常电池。The power lead-acid battery formation, screening and grouping process according to claim 5, characterized in that the abnormal battery whose internal short-circuit voltage does not rise and the battery generates a large amount of heat is judged by means of infrared thermal imaging.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114883674A (en) * | 2022-05-30 | 2022-08-09 | 天能电池集团股份有限公司 | Lead storage battery matching method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105304954A (en) * | 2015-09-30 | 2016-02-03 | 东莞市致格电池科技有限公司 | Battery grouping method and battery grouping system |
| CN106972212A (en) * | 2017-03-28 | 2017-07-21 | 天能电池集团有限公司 | A kind of lead accumulator is internalized into and method for group matching |
| CN107123825A (en) * | 2017-03-28 | 2017-09-01 | 天能电池集团有限公司 | A kind of lead accumulator method for group matching |
| CN109755667A (en) * | 2019-01-11 | 2019-05-14 | 天能电池集团有限公司 | A kind of lead storage battery rapid forming method |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4188268A (en) * | 1978-06-26 | 1980-02-12 | Mizusawa Kagaku Kogyo Kabushiki Kaisha | Process for an electrode for a lead battery |
| CN102347516B (en) * | 2011-10-26 | 2013-07-17 | 浙江天能电池江苏新能源有限公司 | Inner forming process of tubular lead-acid storage battery |
| CN103956523B (en) * | 2014-04-15 | 2016-04-13 | 株洲冶炼集团股份有限公司 | A kind of power car super accumulator formation method |
| CN105186055B (en) * | 2015-09-24 | 2017-12-12 | 浙江天能动力能源有限公司 | A kind of lead-acid accumulator internalized charging method |
| CN106058347B (en) * | 2016-06-30 | 2018-12-14 | 济源市万洋绿色能源有限公司 | A kind of lead-acid accumulator is internalized into pulse charge method |
| CN107887664B (en) * | 2017-09-25 | 2019-08-27 | 天能电池集团股份有限公司 | A kind of lead-acid accumulator microcirculation formation method |
| CN109148815B (en) * | 2018-07-18 | 2021-12-28 | 天能电池集团股份有限公司 | Acidification formation method for long-life lead storage battery |
| CN110797599A (en) * | 2019-10-15 | 2020-02-14 | 江西京九电源（九江）有限公司 | Container formation method of lead-acid storage battery for electric road vehicle |
| CN111092270B (en) * | 2019-11-29 | 2020-12-25 | 天能电池集团股份有限公司 | Lead storage battery formation process optimization method |
-
2020
- 2020-11-04 CN CN202011213243.5A patent/CN112331943B/en active Active
- 2020-11-26 WO PCT/CN2020/131750 patent/WO2022095158A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105304954A (en) * | 2015-09-30 | 2016-02-03 | 东莞市致格电池科技有限公司 | Battery grouping method and battery grouping system |
| CN106972212A (en) * | 2017-03-28 | 2017-07-21 | 天能电池集团有限公司 | A kind of lead accumulator is internalized into and method for group matching |
| CN107123825A (en) * | 2017-03-28 | 2017-09-01 | 天能电池集团有限公司 | A kind of lead accumulator method for group matching |
| CN109755667A (en) * | 2019-01-11 | 2019-05-14 | 天能电池集团有限公司 | A kind of lead storage battery rapid forming method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114883674A (en) * | 2022-05-30 | 2022-08-09 | 天能电池集团股份有限公司 | Lead storage battery matching method |
| CN114883674B (en) * | 2022-05-30 | 2024-05-17 | 天能电池集团股份有限公司 | Lead storage battery matching method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112331943B (en) | 2021-09-24 |
| CN112331943A (en) | 2021-02-05 |
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