CN102751476A - Lithium-manganese anode slurry suitable for coating technology and preparation method thereof - Google Patents
Lithium-manganese anode slurry suitable for coating technology and preparation method thereof Download PDFInfo
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- CN102751476A CN102751476A CN2012102069854A CN201210206985A CN102751476A CN 102751476 A CN102751476 A CN 102751476A CN 2012102069854 A CN2012102069854 A CN 2012102069854A CN 201210206985 A CN201210206985 A CN 201210206985A CN 102751476 A CN102751476 A CN 102751476A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
Lithium-manganese anode slurry suitable for coating technology consists of following components: by weight percentage of total amount, 43 to 48 % of electrolytic manganese dioxide, 1 to 2 % of conductive carbon black, 1 to 2 % of colloid graphite, 0.5 to 1 % of carboxymethylcellulose sodium, 2 to 3 % of styrene-butadiene rubber emulsion and 45 to 50 % of deionized water. The lithium-manganese anode slurry provided by the invention solves problems caused by conventional formulations of a PTFE (polytetrafluoroethylene resin) binder system, so that the slurry is not easy to generate solid-liquid stratification; that the slurry firmly combines an aluminium foil substrate and thus powder of a produced anode plate is not easy to fall off; and that the deionized water, instead of expensive organic solvents, is used as the solvent in the formula to effectively reduce production cost. The invention discloses a method for preparing the anode slurry at the same time.
Description
Technical field
The present invention relates to a kind of disposable lithium-manganese cell field, more particularly it is a kind of lithium manganese anode sizing agent that is applicable to coating process.The invention still further relates to the preparation method of this lithium manganese anode sizing agent.
The background skill
A lithium-manganese cell is widely used in intelligence three table (water meter, ammeter and gas meter) and other industrial instrumentations, the instrument owing to possess high power capacity, high voltage and feature of long life.For improving product quality, reduce production costs and expand the scale of production, utilizing new-type coating process to replace traditional press mold technology is the development trend of lithium-manganese cell industry.The method of two kinds of technology making positive plates is completely different; Requiring difference also very big to anode sizing agent aspect mobile, viscosity and the solid content; With PTFE (polyflon) is that the formula system of adhesive can't make at all and satisfies the slurry that coating requires; The subject matter that wherein exists is that the solid-liquid composition lamination in the slurry is obvious, does not possess enough adhesive force between slurry and the aluminium foil; Cause the positive plate can't moulding, therefore need a kind of suitable prescription of feature development to coating process.
Summary of the invention
The objective of the invention is to overcome above-mentioned existing disadvantages of background technology part, and a kind of lithium manganese anode sizing agent that is applicable to coating process is provided.Its layering of solution anode sizing agent solid-liquid and anodal material and the not enough problem of aluminium foil matrix adhesive force, the while is not caused negative effect to the discharge performance of battery again.
The objective of the invention is to reach through following measure: the positive pole of lithium manganese battery slurry is characterized in that each composition and the percentage by weight in total amount thereof are:
Electrolytic manganese dioxide: 43-48%, conductive black: 1-2%, aquadag 1-2%, sodium carboxymethylcellulose: 0.5-1%, SBR emulsion: 2-3%, deionized water: 45-50%.
In technique scheme, said electrolytic manganese dioxide purity is 91%.
In technique scheme, said SBR emulsion solid content is 60%.
In technique scheme, said electrolytic manganese dioxide: 45kg, conductive black: 1.4kg, aquadag 1.9kg, sodium carboxymethylcellulose: 0.8kg, SBR emulsion: 2.4kg, deionized water: 48.5L (optimized technical scheme).
Be applicable to the preparation method of the lithium manganese anode sizing agent of coating process, it is characterized in that it comprises the steps:
(1), takes by weighing electrolytic manganese dioxide and place that to be cooled to room temperature behind 380 ℃ of baking ovens baking 12h for use;
(2), taking by weighing conductive black and aquadag respectively joins in the electrolytic manganese dioxide powder for use of baking back; Utilize ball mill with three kinds of dry powder blend 2h, mix and to finish and waits for behind the dust settling that the dry powder that mixes is transferred to the metal charging basket of cleaning is for use;
(3), in a clean metal charging basket, inject deionized water, under the stirring at a slow speed of mixer, sodium carboxymethylcellulose is slowly joined in the deionized water, after adding mixing speed is transferred to fast, stir 1h;
(4), treat after sodium carboxymethylcellulose is dissolved in deionized water formation water white transparency thick liquid fully mixing speed to be adjusted to stirring at a slow speed; With material shovel the dry powder gradation that mixes is joined in the thick liquid; Then SBR emulsion is joined in the slurry, regulating mixing speed is fast, continues to stir 2h; Under negative pressure state, stir 0.5h at last at a slow speed and remove bubble, slurry preparation is so far accomplished.
The effect of each component among the present invention comprises but is not limited in electrolytic manganese dioxide and brings into play body as the capacity of anode; Aquadag works to improve the solid phase conductivity of positive mix own as conductive agent; Conductive black improves the absorbency of anodal material, strengthens solid liquid interface conductivity; Butadiene-styrene rubber is as main adhesive; Sodium carboxymethylcellulose is as thickener, and aid adhesion and dispersion, improves the viscosity of positive pole of lithium manganese battery slurry, make it to be prone to be attached to the aluminium foil matrix surface, and the difficult deposition of slurry makes Separation of Solid and Liquid.
The present invention has mainly solved following problem for the conventional formulation of PTFE (polyflon) binder system: 1. slurry is not prone to the solid-liquid lamination; 2. slurry and aluminium foil matrix bond are firm, and the positive plate of making is difficult for dry linting; 3. solvent is a deionized water in the prescription, does not use expensive organic solvents, effectively reduces production cost.
Description of drawings
The a collection of battery capacity data normal distribution curve figure that Fig. 1 adopts press mold technology to make for conventional formulation.
The a collection of battery capacity data normal distribution curve figure that Fig. 2 fills a prescription and adopts coating process to make for the present invention.
Fig. 3 is the discharge correlation curve figure of the CR123A battery that adopts conventional formulation and the present invention to fill a prescription to make, and wherein curve 1 is the battery discharge curve of conventional formulation making, and curve 2 is the fill a prescription battery discharge curve of making of the present invention.
Embodiment
Specify performance of the present invention below in conjunction with accompanying drawing, but they do not constitute to qualification of the present invention, only do for example.Simultaneously through explaining that advantage of the present invention will become clear more and easy and understand.
Being explained as follows wherein about the several technical terms among Fig. 1, Fig. 2:
The capacity average is meant the mean value of same a collection of test cell capacity to be detected;
The battery sample number refers to this batch battery sum of being detected;
Standard deviation is meant the average of the distance of each capacity data deviation average, can reflect the dispersion degree of a data set, and the more little expression data of standard deviation distribute even more;
Process Capability Index C
PKBe the index that modern enterprise is used to represent the processing procedure ability, its numerical value is big more, and then the dispersion of product quality characteristics value is just more little, and product quality is stable more, otherwise then the dispersion of product quality characteristics value is just big more, and the product quality fluctuation is big more.
Consulting accompanying drawing 1 can know: 85 CR123A batteries that adopt conventional formulation and the making of press mold technology are 1387.66mAh with the average size of 10mA constant-current discharge; The non-constant width of distributed area; Be 1000 ~ 1600mAh; Capacity uniformity is very undesirable, and the capacity data standard deviation has reached 77.7972, Process Capability Index C
PKBe 0.80;
Consulting accompanying drawing 2 can know: 55 CR123A batteries that adopt invention prescription and coating process making are 1442.97mAh with the average size of 10mA constant-current discharge; It is relatively concentrated to distribute; Be 1350 ~ 1530mAh; Capacity mean value and uniformity all have very big lifting, and the capacity data standard deviation is reduced to 33.4951, Process Capability Index C
PKRise to 1.56;
Consulting accompanying drawing 3 can know: the battery that adopts invention prescription and coating process to make is the lifting that certain degree is all arranged on discharge platform voltage or discharge capacity.
The present invention is applicable to the lithium manganese anode sizing agent of coating process; It is made up of following component, and the percentage by weight of each composition in total amount is: electrolytic manganese dioxide: 43-48%, conductive black: 1-2%; Aquadag 1-2%; Sodium carboxymethylcellulose: 0.5-1%, SBR emulsion: 2-3%, deionized water: 45-50%.Described electrolytic manganese dioxide purity is 91%, and said SBR emulsion solid content is 60%.
Preferably: electrolytic manganese dioxide: 45kg, conductive black: 1.4kg, aquadag 1.9kg, sodium carboxymethylcellulose: 0.8kg, SBR emulsion: 2.4kg, deionized water: 48.5L
According to the above-mentioned preparation method who is applicable to the lithium manganese anode sizing agent of coating process, it comprises the steps:
(1), takes by weighing electrolytic manganese dioxide and place that to be cooled to room temperature behind 380 ℃ of baking ovens baking 12h for use;
(2), taking by weighing conductive black and aquadag respectively joins in the electrolytic manganese dioxide powder for use of baking back; Utilize ball mill with three kinds of dry powder blend 2h, mix and to finish and waits for behind the dust settling that the dry powder that mixes is transferred to the metal charging basket of cleaning is for use;
(3), in a clean metal charging basket, inject deionized water, under the stirring at a slow speed of mixer, sodium carboxymethylcellulose is slowly joined in the deionized water, after adding mixing speed is transferred to fast, stir 1h;
(4), treat after sodium carboxymethylcellulose is dissolved in deionized water formation water white transparency thick liquid fully mixing speed to be adjusted to stirring at a slow speed; With material shovel the dry powder gradation that mixes is joined in the thick liquid; Then SBR emulsion is joined in the slurry, regulating mixing speed is fast, continues to stir 2h; Under negative pressure state, stir 0.5h at last at a slow speed and remove bubble, slurry preparation is so far accomplished.
Embodiment 1
Be applicable to the lithium manganese anode sizing agent of coating process: form by following component; The percentage by weight of each composition in total amount is: electrolytic manganese dioxide: 45kg; Conductive black: 1.4kg, aquadag 1.9kg, sodium carboxymethylcellulose: 0.8kg; SBR emulsion: 2.4kg, deionized water: 48.5L.Wherein electrolytic manganese dioxide purity is 91%, and wherein the SBR emulsion solid content is 60%.
Be applicable to the preparation method of the lithium manganese anode sizing agent of coating process, it comprises the steps:
1, takes by weighing the 45kg electrolytic manganese dioxide and place that to be cooled to room temperature behind 380 ℃ of baking ovens baking 12h for use;
2, taking by weighing the conductive black of 1.4kg and the aquadag of 1.9kg respectively joins in the electrolytic manganese dioxide powder for use of baking back; Utilize ball mill with three kinds of dry powder blend 2h, mix and to finish and waits for behind the dust settling that the dry powder that mixes is transferred to the metal charging basket of cleaning is for use;
3, in a clean metal charging basket, inject the 48.5L deionized water, the 0.8kg sodium carboxymethylcellulose that under the stirring at a slow speed of mixer, will take by weighing in advance slowly joins in the deionized water, after adding mixing speed is transferred to fast, stirs 1h;
4, treat after sodium carboxymethylcellulose is dissolved in deionized water formation water white transparency thick liquid fully mixing speed to be adjusted to stirring at a slow speed; With material shovel the dry powder gradation that mixes is joined in the thick liquid; Take by weighing the 2.4kg SBR emulsion then and join in the slurry, regulating mixing speed is fast, continues to stir 2h; Under negative pressure state, stir 0.5h at last at a slow speed and remove bubble, slurry preparation is so far accomplished.
Embodiment 2
Be applicable to the lithium manganese anode sizing agent of coating process: be made up of following component, the percentage by weight of each composition in total amount is: electrolytic manganese dioxide: 43kg, conductive black: 2kg; Aquadag 1kg; Sodium carboxymethylcellulose: 1kg, SBR emulsion: 2kg, deionized water: 50L.Wherein electrolytic manganese dioxide purity is 91%, and wherein the SBR emulsion solid content is 60%.
The preparation method is with embodiment 1.
Embodiment 3
Be applicable to the lithium manganese anode sizing agent of coating process: form by following component; The percentage by weight of each composition in total amount is: electrolytic manganese dioxide: 48kg (kilogram); Conductive black: 1kg, aquadag 2kg, sodium carboxymethylcellulose: 0.5kg; SBR emulsion: 3kg, deionized water: 45L (liter).Wherein electrolytic manganese dioxide purity is 91%, and wherein the SBR emulsion solid content is 60%.
The preparation method is with embodiment 1.
Detect through experiment: the slurry with above-mentioned prescription and technology preparation is made into lithium manganese CR123A battery; The lifting of manganese dioxide ratio and coating process are compared to the huge advantage of traditional press mold technology on precision in having benefited from filling a prescription, and test cell is still all possessing remarkable advantages on batch cell integrated uniformity on single the discharge performance.
Claims (5)
1. be applicable to the lithium manganese anode sizing agent of coating process; It is characterized in that it is made up of following component, the percentage by weight of each composition in total amount is: electrolytic manganese dioxide: 43-48%, conductive black: 1-2%; Aquadag 1-2%; Sodium carboxymethylcellulose: 0.5-1%, SBR emulsion: 2-3%, deionized water: 45-50%.
2. the lithium manganese anode sizing agent that is applicable to coating process according to claim 1 is characterized in that described electrolytic manganese dioxide purity is 91%.
3. the lithium manganese anode sizing agent that is applicable to coating process according to claim 1 and 2 is characterized in that said SBR emulsion solid content is 60%.
4. the lithium manganese anode sizing agent that is applicable to coating process according to claim 1 is characterized in that said electrolytic manganese dioxide: 45kg, conductive black: 1.4kg; Aquadag 1.9kg; Sodium carboxymethylcellulose: 0.8kg, SBR emulsion: 2.4kg, deionized water: 48.5L.
5. according to the described preparation method who is applicable to the lithium manganese anode sizing agent of coating process of above-mentioned arbitrary claim, it is characterized in that it comprises the steps:
(1), takes by weighing electrolytic manganese dioxide and place that to be cooled to room temperature behind 380 ℃ of baking ovens baking 12h for use;
(2), taking by weighing conductive black and aquadag respectively joins in the electrolytic manganese dioxide powder for use of baking back; Utilize ball mill with three kinds of dry powder blend 2h, mix and to finish and waits for behind the dust settling that the dry powder that mixes is transferred to the metal charging basket of cleaning is for use;
(3), in a clean metal charging basket, inject deionized water, under the stirring at a slow speed of mixer, sodium carboxymethylcellulose is slowly joined in the deionized water, after adding mixing speed is transferred to fast, stir 1h;
(4), treat after sodium carboxymethylcellulose is dissolved in deionized water formation water white transparency thick liquid fully mixing speed to be adjusted to stirring at a slow speed; With material shovel the dry powder gradation that mixes is joined in the thick liquid; Then SBR emulsion is joined in the slurry, regulating mixing speed is fast, continues to stir 2h; Under negative pressure state, stir 0.5h at last at a slow speed and remove bubble, slurry preparation is so far accomplished.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103682246A (en) * | 2013-12-13 | 2014-03-26 | 武汉昊诚能源科技有限公司 | High load Li-Mn battery and preparation method thereof |
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Patent Citations (6)
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| JPS5676165A (en) * | 1979-11-26 | 1981-06-23 | Matsushita Electric Ind Co Ltd | Manufacture of organic-electrolyte battery |
| CN101183731A (en) * | 2007-12-14 | 2008-05-21 | 山东海霸通讯设备有限公司 | Lithium iron phosphate aluminum shell 10 ampere-hour column battery and producing technique thereof |
| CN102057522A (en) * | 2008-07-25 | 2011-05-11 | 松下电器产业株式会社 | Bipolar cell |
| CN101997124A (en) * | 2009-08-19 | 2011-03-30 | 韩国电子通信研究院 | Vacuum sealing type primary film battery and method of manufacturing the same |
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| CN103682246A (en) * | 2013-12-13 | 2014-03-26 | 武汉昊诚能源科技有限公司 | High load Li-Mn battery and preparation method thereof |
| CN103682246B (en) * | 2013-12-13 | 2016-03-16 | 武汉昊诚能源科技有限公司 | A kind of high load Li-Mn battery and preparation method thereof |
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Effective date of registration: 20200618 Address after: 430040, No. 1, Taichung Avenue, Gaoqiao Industrial Park, Wu Shan Economic Development Zone, Hubei, Wuhan Co-patentee after: Beijing Nandu Haocheng power equipment LLC Patentee after: WUHAN HAOCHENG ENERGY RESOURCES TECHNOLOGY Co.,Ltd. Address before: 430040 Hubei province Dongxihu District of Wuhan City Lake Science and Technology Industry Development Park No. 18 Patentee before: WUHAN HAOCHENG ENERGY RESOURCES TECHNOLOGY Co.,Ltd. |
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Address after: 430040 No.1, Taichung Avenue, Gaoqiao Industrial Park, Wujiashan Economic Development Zone, Wuhan City, Hubei Province Patentee after: Wuhan Haocheng lithium Technology Co.,Ltd. Patentee after: Beijing Nandu Haocheng power equipment LLC Address before: 430040 No.1, Taichung Avenue, Gaoqiao Industrial Park, Wujiashan Economic Development Zone, Wuhan City, Hubei Province Patentee before: WUHAN HAOCHENG ENERGY RESOURCES TECHNOLOGY Co.,Ltd. Patentee before: Beijing Nandu Haocheng power equipment LLC |