KR101737320B1 - Manufacturing method of active material for lead-acid battery - Google Patents
Manufacturing method of active material for lead-acid battery Download PDFInfo
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- KR101737320B1 KR101737320B1 KR1020150149930A KR20150149930A KR101737320B1 KR 101737320 B1 KR101737320 B1 KR 101737320B1 KR 1020150149930 A KR1020150149930 A KR 1020150149930A KR 20150149930 A KR20150149930 A KR 20150149930A KR 101737320 B1 KR101737320 B1 KR 101737320B1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
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Abstract
본 발명은 납출전지의 활물질 제조 방법에 관한 것으로, 납축전지용 활물질에 납축전지 활물질 접착력 개선용으로 셀룰로오스 나노화이버 (Nano Fiber)를 첨가 하여, 납축전지의 활물질 탈락현상을 방지하고 반응표면적을 증대시켜 납축전지의 기대 수명을 향상시키게 하는 것임. The present invention relates to a method of producing an active material for lead-acid batteries, and a method of adding a cellulose nano fiber to an active material for a lead-acid battery to improve the adhesion of the lead-acid battery active material to prevent detachment of the active material of the lead- Thereby improving the life expectancy of the lead-acid battery.
Description
본 발명은 납축전지의 활물질 제조 방법에 관한 것으로 특히 활물질에 단섬유를 혼합하여 활물질을 제조하는 방법에 관한 것이다.
The present invention relates to a method of manufacturing an active material for a lead-acid battery, and more particularly, to a method for manufacturing an active material by mixing short fibers with an active material.
현재 납축전지 활물질 메커니즘은 활물질에 물리적 강도 및 황산과의 반응 표면적 확보를 위하여 폴리에스터 계열 화이버를 첨가 하고 있다.At present, the lead acid battery active material mechanism adds polyester fiber to the active material to secure physical strength and reaction surface area with sulfuric acid.
통상적으로 납축전지 활물질에 2~5 데니어의 섬도를 갖고, 1~10밀리 길이의 폴리에스터 계열의 화이버를 첨가 하는데 이러한 섬유(화이버)는 내산성과 내산화성이 우수한 특징이 있다. 이 때 첨가되는 유기합성 단섬유는 통상적으로 원형 단면 형태를 가지며, 길이는 2 ~10밀리미터 정도이다. 유기합성 단섬유의 성분은 내산성 및 내산화성이 우수한 폴리프로필렌, 폴리에스테르, 모드아크릴 계열이 주종을 이루고 있다.Generally, lead-acid battery active materials have a fineness of 2 to 5 denier, and polyester fibers of 1 to 10 millimeters in length are added. These fibers (fibers) are characterized by excellent acid resistance and oxidation resistance. Organic synthetic staple fibers added at this time usually have a circular cross-sectional shape, and the length is about 2 to 10 millimeters. Organic synthetic staple fibers are mainly composed of polypropylene, polyester and mode acrylic which are excellent in acid resistance and oxidation resistance.
특허 제10-0603908호 “축전지용 극판 및 그 제조 방법”은 활물질 표면에 섬유필라멘트가 박히도록 섬유강화 종이를 압력을 가해 부착하고 표면의 요철부에 활물질을 충전하여서 되는 극판 제조 방법을 개시한다. 제10-0603908호는 축전지의 극판과 그 제조방법에 관한 것으로서 축전지의 극판은 전기가 흐르는 통로 역할을 하는 기판에 전기화학적 활성을 갖는 활물질이 도포되고, 그 활물질 표면에 섬유강화종이를 부착 또는 압착하는 단계에서 섬유강화종이의 섬유 필라멘트가 일정깊이로 박히도록 압력을 가해 부착하고, 섬유강화종이의 표면 요철부에 활물질이 충전되어 그 결착표면적을 증대시킴으로서, 기판으로부터 활물질이 탈리되는 것을 방지하고, 나아가, 섬유강화종이의 다공성으로 인한 극판의 초기고율방전 특성을 향상시키고 또한 섬유강화종이의 섬유필라멘트 조직의 안정된 지지력과 내산성으로 인한 활물질을 잘 보유하고 지지함으로서 축전지의 수명을 연장시키는 기술에 관한 것이다. 이 발명은 활물질의 탈락 방지에 탁월한 작용을 한다. 그러나, 섬유강화 종이는 그 표면의 요철부에 충전한 활물질의 탈락 염려를 증가시키며 섬유로 인한 황산과의 반응 장애 염려를 배제할 수 없다.
Patent No. 10-0603908 discloses a method for manufacturing an electrode plate in which a fiber-reinforced paper is pressed while the fiber filaments are stuck on the surface of the active material, and the active material is filled in the irregularities on the surface. No. 10-0603908 relates to an electrode plate of a battery and a method of manufacturing the same. The electrode plate of the battery is coated with an active material having electrochemical activity on a substrate serving as a passage through which electricity flows, and a fiber- The active material is filled in the surface irregularities of the fiber-reinforced paper to increase the binding surface area thereof, thereby preventing the active material from being separated from the substrate, Further, the present invention relates to a technique for improving the initial high-rate discharging characteristics of the electrode plate due to the porosity of the fiber-reinforced paper, and also for retaining and supporting the active material due to the stable supporting force and acid resistance of the fiber filament structure of the fiber- . This invention has an excellent effect in preventing the active material from falling off. However, the fiber-reinforced paper increases the fear of peeling off the active material packed in the irregularities on the surface thereof, and can not exclude the possibility that the fibers are likely to react with sulfuric acid.
본 발명이 해결하려는 과제는 고온 환경에서 잦은 충전 및 방전시 활물질 탈락에 의하여 배터리의 수명이 종지되는 현상을 개선하여야 한다는 것이다. 보다 자세히 언급하면 배터리의 고장 원인은 사용 중에 부하의 종류와 관리하는 방법에 따라 좌우된다. 주된 고장요인은 양극 활물질 탈락, 음극 활물질 파손, 양극 격자부식, 격리판 파손, 위 요인들의 복합적인 요인 등이 있다. 특히 자동차에 장착된 제품의 경우 운행 조건 및 전기 장치의 사용 부하에 따라 활물질 탈락이 가속화 되어 조기 수명 종지 현상이 발생된다. 따라서 전극의 활물질을 지지하게 만드는 일이 중요하며, 납축전지 업계에서는 활물질 지지력을 향상시키는 연구가 활발하게 진행 중이다. 본 발명이 해결하려는 과제는 활물질의 지지력을 향상시켜 상기 고장 요인 중 양극 활물질 탈락, 음극 활물질 파손에 의한 조기 수명종지를 개선하는 것이다.
The problem to be solved by the present invention is to improve the lifetime of the battery due to the removal of the active material during frequent charging and discharging in a high temperature environment. More specifically, the cause of battery failure depends on the type of load and how it is managed during use. The major failure factors are detachment of cathode active material, anode active material damage, anodic lattice corrosion, breakdown of separator, and a combination of the above factors. Particularly, in the case of a product mounted on an automobile, the deterioration of the active material accelerates according to the operating conditions and the usage load of the electric device, resulting in the premature life termination phenomenon. Therefore, it is important to support the active material of the electrode. In the lead-acid battery industry, researches are actively conducted to improve the active material bearing capacity. The problem to be solved by the present invention is to improve the bearing capacity of the active material, thereby improving deterioration of the life of the cathode due to detachment of the cathode active material and breakage of the anode active material.
위와 같은 과제를 해결하기 위하여, 연분, 황산, 양극이나 음극에 따른 첨가제 및 단섬유를 혼합하고 숙성 건조하여 활물질을 제조함에 있어서, 본발명은, 혼합되는 상기 단섬유가 0.1~0.5 De 사이즈의 셀룰로오스 나노 화이버(Fiber)인 것을 특징으로 하는 납축전지의 극판용 활물질 제조방법을 제공한다.In order to solve the above problems, the present invention provides a process for producing an active material by mixing starch, sulfuric acid, an additive according to an anode or a cathode, and short fibers and aging and drying the mixture, Wherein the anode active material is a nanofiber fiber.
위와 같은 본 발명은, 반응표면적을 높이고 저항을 감소시키며 전도도 특성을 개선시켜, 결과적으로 활물질의 효율을 향상 시키며, 납축전지의 기대수명을 향상시킬 수 있는 효과가 있다.
The present invention has the effect of increasing the surface area of the reaction, reducing the resistance, improving the conductivity, improving the efficiency of the active material, and improving the life expectancy of the lead-acid battery.
도 1은 미국 자동차 기술자 협회 규격에 따라 75℃ 환경에서 수명을 검증한 그래프 (SAE J240) 이다. FIG. 1 is a graph (SAE J240) showing a life test at 75.degree. C. according to the American Automotive Engineers Association standard.
이하 첨부된 도면을 참조하여 본 발명을 상세히 설명한다. BRIEF DESCRIPTION OF THE DRAWINGS FIG.
본 발명은 연분, 황산, 양극과 음극 각각에 따른 공지의 첨가제, 및, 단섬유를 혼합하고 숙성 건조하여 활물질을 제조함에 있어서, 본발명은, 혼합되는 상기 단섬유는 0.1~0.5 De 사이즈의 셀룰로오스 나노 화이버(Fiber)인 것을 특징으로 하는 납축전지의 극판용 활물질 제조방법을 제공한다.
즉, 본 발명은 연분, 황산, 양극과 음극 각각에 따른 첨가제, 및, 단섬유를 혼합하여 혼합물을 제조하는 단계;
상기 제조된 혼합물을 숙성 건조하는 단계;
를 포함하는 납축전지의 극판용 활물질 제조방법에 있어서,
상기 연분, 황산, 양극과 음극 각각에 따른 첨가제, 및, 단섬유를 혼합하여 혼합물을 제조하는 단계에서 혼합되는 상기 단섬유가 0.1~0.5 De 사이즈의 셀룰로오스 나노 화이버(Fiber)인 납축전지의 활물질 제조방법을 제공한다.In the present invention, in the production of an active material by mixing known materials such as fuels, sulfuric acid, a positive electrode and a negative electrode, and short fibers, followed by aging and drying, the short fibers are mixed with a cellulose having a size of 0.1 to 0.5 De Wherein the anode active material is a nanofiber fiber.
That is, the present invention relates to a method for producing a mixture, which comprises mixing a starch, sulfuric acid, an additive according to each of an anode and a cathode, and short fibers to prepare a mixture;
Aging and drying the prepared mixture;
The method comprising the steps of:
The active material of the lead-acid battery is a cellulose nanofiber having a size of 0.1 to 0.5 De in the short fibers mixed in the step of preparing the mixture by mixing the fuels, sulfuric acid, additives according to each of the positive and negative electrodes, and short fibers. ≪ / RTI >
종래의 활물질에 혼합하던 단섬유에 갈음하여 혼합하여, 본 발명은 셀룰로오스 나노 화이버(Nano Fiber)를 혼합하되 종래에 있어서와 같은 중량의 나노화이버(Nano Fiber) 섬유를 활물질에 혼합함으로서 더 많은 부피량을 혼합할 수 있어 활물질 내 황산과의 반응 면적을 확대시켜, 납축전지의 성능 특히 기대 수명을 향상시킬 수 있는 효과가 있다.The present invention relates to a method of mixing cellulose nanofibers with nanofibers of the same weight as conventional ones by mixing them with the active material, It is possible to increase the reaction area with the sulfuric acid in the active material, thereby improving the performance of the lead-acid battery, especially the life expectancy.
상기 셀룰로오스 나노화이버(Nano Fiber)는 양극과 음극에 따른 상기 첨가제 전체 혼합물 대비 0.1~1wt%인 것이 바람직하다.It is preferable that the cellulose nanofiber is 0.1 to 1 wt% of the total mixture of the additives according to the positive electrode and the negative electrode.
상기 단섬유인 나노 화이버는 셀룰로오스 계열로, 0.5 데니어의 나노화이버를 말한다. 본 발명은, 셀룰로오스 나노 화이버 (Nano Fiber)를 기존 중량 대비 많은 양이 활물질에 첨가되고 반응표면적을 높이고 저항을 감소, 전도도 특성이 개선되어, 결과적으로 활물질의 효율을 향상 시키며, 납축전지의 기대수명 향상을 얻을 수 있는 것으로 발견 하였다. The monofilament nanofibers are cellulose-based nanofibers of 0.5 denier. Disclosure of Invention Technical Problem [8] The present invention relates to a method for manufacturing a lead-acid battery, in which a large amount of a cellulose nanofiber is added to an active material to increase the reaction surface area, reduce resistance, improve conductivity, Improvement can be obtained.
고온에서의 수명을 검증하기 위해 SAE J240 규격에 따라 수명 시험을 진행하였다.The life test was conducted according to the SAE J240 standard to verify the lifetime at high temperature.
상기 시험 규격은 납축전지가 고온(75℃)에서 충전과 방전을 반복하여 수명이 종지될 때까지의 사이클을 측정하는 시험 방법이다. (1 사이클 : 25A 4분 방전, 14.8V[최대 25A] 정전압 10분 충전)The test standard is a test method for measuring the cycle until the life of the lead-acid battery is terminated by repeating charging and discharging at high temperature (75 ° C). (1 cycle: 25A 4 minute discharge, 14.8V [25A maximum] Constant voltage 10 minutes charge)
복하며, 7.2V 이하이면 배터리를 수명종지로 판정하여, 시험을 중단한다If it is below 7.2V, the battery is determined to be the end of life and the test is stopped
시험 결과 표1 및 도1에 도시된 바와 같이 본 발명의 활물질을 사용한 축전지(도1:실시예; 도2:개선)는 2,400 사이클에서 종지되었으며, 이는 종래예(기존) 대비 25% 향상되었다. Test Results As shown in Table 1 and Fig. 1, the battery using the active material of the present invention (Fig. 1: Example: Fig. 2: improvement) was terminated at 2,400 cycles, which was improved by 25% compared to the conventional example (existing).
표1은 미국 자동차 기술자 협회 규격에 따라 75℃ 환경에서 수명을 검증한 시험결과 (SAE J240) 이다.Table 1 is the test result (SAE J240) which verifies the life at 75 ℃ environment according to American Automobile Engineers Association standard.
또한, 본 발명의 활물질을 사용한 납축전지는, 납축전지 성능 중 고율방전특성이 향상 됨을 확인 하였다. In addition, it was confirmed that the lead acid battery using the active material of the present invention improved the high rate discharge characteristics among the lead battery cells.
도 2는 미국 자동차 기술자 협회 규격에 따라 75℃ 환경에서 수명을 검증한 그래프 (SAE J240) 이다. 상기 시험 규격은 납축전지가 고온(75℃)에서 충전과 방전을 반복하여 수명이 종지될 때까지의 사이클을 측정하는 시험 방법이다. (1 사이클 : 25A 4분 방전, 14.8V[최대 25A] 정전압 10분 충전)FIG. 2 is a graph (SAE J240) that verifies the lifetime in a 75.degree. The test standard is a test method for measuring the cycle until the life of the lead-acid battery is terminated by repeating charging and discharging at high temperature (75 ° C). (1 cycle: 25A 4 minute discharge, 14.8V [25A maximum] Constant voltage 10 minutes charge)
본 시험은 1주 동안 480회 반복하며 그 후 56시간 정치 후 630A 고율로 방전하여 30초 시점에서의 전압을 측정함으로써 배터리의 상태를 판정한다. 30초 시점의 전압이 7.2V 이상이면 배터리를 온전한 상태로 판정하여 위의 사이클을 반복하며, 7.2V 이하이면 배터리를 수명종지로 판정하여, 시험을 중단한다. 도2의 그래프에 나타난 바와 같이 본 발명은 960사이클 이상부터 종래의 것에 비해 현격하게 높은 전압이 측정됨을 확인할 수 있다.
This test is repeated 480 times for 1 week, after which it is discharged for 630A at a high rate after standing for 56 hours and the voltage at 30 seconds is measured to determine the state of the battery. If the voltage at the time of 30 seconds is above 7.2V, the battery is judged as being fully charged and the above cycle is repeated. If the voltage is below 7.2V, the battery is determined as the end of life and the test is stopped. As shown in the graph of FIG. 2, it can be seen that the present invention has a significantly higher voltage measured from 960 cycles to over the conventional one.
본 발명을 첨부된 도면과 함께 설명하였으나, 이는 본 발명의 요지를 포함하는 다양한 실시 형태 중의 하나의 실시예에 불과하며, 당업계에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 하는 데에 그 목적이 있는 것으로, 본 발명은 상기 설명된 실시예에만 국한되는 것이 아님은 명확하다. 따라서, 본 발명의 보호범위는 하기의 청구범위에 의해 해석되어야 하며, 본 발명의 요지를 벗어나지 않는 범위 내에서의 변경, 치환, 대체 등에 의해 그와 동등한 범위 내에 있는 모든 기술 사상은 본 발명의 권리범위에 포함될 것이다. 또한, 도면의 일부 구성은 구성을 보다 명확하게 설명하기 위한 것으로 실제보다 과장되거나 축소되어 제공된 것임을 명확히 한다. 또한, 청구항 부호는 이해를 돕기 위한 것일 뿐 본 발명의 형상과 구조를 첨부된 도면에 한정한다는 뜻이 아니다.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it should be understood that various changes and modifications will be apparent to those skilled in the art. It is to be understood that the present invention is not limited to the above-described embodiments. Accordingly, the scope of protection of the present invention should be construed according to the following claims, and all technical ideas which fall within the scope of equivalence by alteration, substitution, substitution and the like within the scope of the present invention, Range. In addition, it should be clarified that some configurations of the drawings are intended to explain the configuration more clearly and are provided in an exaggerated or reduced size than the actual configuration. It is to be understood that the appended claims are intended to facilitate understanding only and do not limit the shape and construction of the present invention to the accompanying drawings.
Claims (2)
상기 제조된 혼합물을 숙성 건조하는 단계;
를 포함하는 납축전지의 극판용 활물질 제조방법에 있어서,
상기 연분, 황산, 양극과 음극 각각에 따른 첨가제, 및, 단섬유를 혼합하여 혼합물을 제조하는 단계에서 혼합되는 상기 단섬유가 0.1~0.5 De 사이즈의 셀룰로오스 나노 화이버(Fiber)이며,
상기 셀룰로오스 나노화이버(Nano Fiber)의 첨가비는 상기 혼합물 대비 0.1~1wt%인 것을 특징으로 하는 납축전지의 활물질 제조방법.
Preparing an admixture of sulfuric acid, an additive according to each of an anode and a cathode, and short fibers to prepare a mixture;
Aging and drying the prepared mixture;
The method comprising the steps of:
The short fibers to be mixed in the step of mixing the fuels, sulfuric acid, the additives according to each of the positive electrode and the negative electrode, and the short fibers in the preparation of the mixture are cellulose nano fibers having a size of 0.1 to 0.5 De,
Wherein the addition ratio of the cellulose nanofibers is 0.1 to 1 wt% to the mixture.
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