CN102751476B - 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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- CN102751476B CN102751476B CN201210206985.4A CN201210206985A CN102751476B CN 102751476 B CN102751476 B CN 102751476B CN 201210206985 A CN201210206985 A CN 201210206985A CN 102751476 B CN102751476 B CN 102751476B
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- 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
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- Y02E60/10—Energy storage using batteries
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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 being applicable to coating process.The invention still further relates to the preparation method of this lithium manganese anode sizing agent.
Background skill
A lithium-manganese cell, owing to possessing high power capacity, high voltage and long-life feature, is widely used in intelligence three table (water meter, ammeter and gas meter) and other industrial instrumentations, instrument.For improving product quality, reduce production cost and expanding the scale of production, utilize new-type coating process to replace development trend that traditional press mold technique is lithium-manganese cell industry.The method of two kinds of technique making positive plates is completely different, also very large to the requirement difference of anode sizing agent in mobility, viscosity and solid content, with PTFE(polyflon) slurry meeting coating and require cannot be made for the formula system of adhesive at all, the subject matter wherein existed is, solid-liquid composition lamination in slurry is obvious, enough adhesive force is not possessed between slurry and aluminium foil, cause positive plate cannot be shaping, therefore need a kind of suitable formula of feature development for coating process.
Summary of the invention
The object of the invention is to the weak point overcoming above-mentioned existing background technology, and a kind of lithium manganese anode sizing agent being applicable to coating process is provided.It solves the inadequate problem of anode sizing agent solid-liquid layering and anode material and foil substrate adhesive force, does not cause negative effect again to the discharge performance of battery simultaneously.
The object of the invention is to be reached by following measure: 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, described electrolytic manganese dioxide purity is 91%.
In technique scheme, described SBR emulsion solid content is 60%.
In technique scheme, described electrolytic manganese dioxide: 45kg, conductive black: 1.4kg, aquadag 1.9kg, sodium carboxymethylcellulose: 0.8kg, SBR emulsion: 2.4kg, the preferred technical scheme of deionized water: 48.5L().
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), take electrolytic manganese dioxide and be placed in that to be cooled to room temperature after 380 DEG C of baking ovens toast 12h stand-by;
(2), take respectively conductive black and aquadag join baking after in stand-by electrolytic manganese dioxide powder, utilize ball mill by three kinds of dry powder blend 2h, mix complete and after waiting for dust settling, the dry powder mixed to be transferred to clean metal charging basket stand-by;
(3), in a clean metallic charging basket inject deionized water, under the low rate mixing of mixer, sodium carboxymethylcellulose is slowly joined in deionized water, mixing speed is adjusted to fast after adding, stir 1h;
(4), be dissolved in completely after deionized water forms water white transparency thick liquid until sodium carboxymethylcellulose mixing speed is adjusted to low rate mixing, the dry powder gradation mixed joins in thick liquid by materials shovel, then SBR emulsion is joined in slurry, mixing speed is regulated to be quick, Keep agitation 2h, finally under negative pressure state, low rate mixing 0.5h removes bubble, and so far slurry preparation completes.
The effect of each component in the present invention, including but not limited to the capacity performance body of electrolytic manganese dioxide as anode; Aquadag, as conductive agent, plays a part to improve the solid phase conductivity of positive mix own; Conductive black improves the absorbency of anode 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, makes it easily to be attached to foil substrate surface, and slurry not easily precipitates and makes Separation of Solid and Liquid.
The present invention is relative to PTFE(polyflon) mainly solve following problem for the conventional formulation of binder system: 1. not easily there is solid-liquid lamination in slurry; 2. slurry is combined firmly with foil substrate, the positive plate made not easily dry linting; 3. in formula, solvent is deionized water, does not use expensive organic solvent, effectively reduces production cost.
Accompanying drawing explanation
Fig. 1 is a collection of battery capacity data normal distribution curve figure that conventional formulation adopts the making of press mold technique.
Fig. 2 be the present invention fill a prescription adopt coating process make a collection of battery capacity data normal distribution curve figure.
Fig. 3 adopts conventional formulation and the present invention to fill a prescription the electric discharge correlation curve figure of the CR123A battery made, wherein the battery discharge curve that makes for conventional formulation of curve 1, and curve 2 to be filled a prescription the battery discharge curve of making for the present invention.
Embodiment
Describe performance of the present invention in detail below in conjunction with accompanying drawing, but they do not form limitation of the invention, only for example.Simultaneously by illustrating that advantage of the present invention will become clearly and easy understand.
Being explained as follows wherein about the several technical terms in Fig. 1, Fig. 2:
Capacity average refers to the mean value of detected same a collection of test cell capacity;
Battery sample number refers to this batch of detected battery sum;
Standard deviation refers to the average of the distance of each capacity data deviation average, can reflect the dispersion degree of a data set, and standard deviation less expression Data distribution8 is more even;
Measure of Process Capability C
pKbe modern enterprise for representing the index of process capability, its numerical value is larger, then the dispersion of product quality characteristics value is less, and product quality is more stable, otherwise then the dispersion of product quality characteristics value is larger, product quality fluctuation larger.
Accompanying drawings 1 is known: 85 adopt the CR123A battery of conventional formulation and the making of press mold technique with the average size of 10mA constant-current discharge for 1387.66mAh, the non-constant width of distributed area, be 1000 ~ 1600mAh, capacity uniformity is very undesirable, capacity data standard deviation reaches 77.7972, Measure of Process Capability C
pKbe 0.80;
Accompanying drawings 2 is known: 55 adopt the CR123A battery of invention formula and coating process making with the average size of 10mA constant-current discharge for 1442.97mAh, distribute relatively concentrated, be 1350 ~ 1530mAh, capacity mean value and uniformity have very large lifting, capacity data standard deviation is reduced to 33.4951, Measure of Process Capability C
pKrise to 1.56;
Accompanying drawings 3 is known: the battery adopting invention formula and coating process to make is the lifting all having certain degree 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, 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 described 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 being applicable to the lithium manganese anode sizing agent of coating process, it comprises the steps:
(1), take electrolytic manganese dioxide and be placed in that to be cooled to room temperature after 380 DEG C of baking ovens toast 12h stand-by;
(2), take respectively conductive black and aquadag join baking after in stand-by electrolytic manganese dioxide powder, utilize ball mill by three kinds of dry powder blend 2h, mix complete and after waiting for dust settling, the dry powder mixed to be transferred to clean metal charging basket stand-by;
(3), in a clean metallic charging basket inject deionized water, under the low rate mixing of mixer, sodium carboxymethylcellulose is slowly joined in deionized water, mixing speed is adjusted to fast after adding, stir 1h;
(4), be dissolved in completely after deionized water forms water white transparency thick liquid until sodium carboxymethylcellulose mixing speed is adjusted to low rate mixing, the dry powder gradation mixed joins in thick liquid by materials shovel, then SBR emulsion is joined in slurry, mixing speed is regulated to be quick, Keep agitation 2h, finally under negative pressure state, low rate mixing 0.5h removes bubble, and so far slurry preparation completes.
Embodiment 1
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: 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 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, take 45kg electrolytic manganese dioxide and be placed in that to be cooled to room temperature after 380 DEG C of baking ovens toast 12h stand-by;
The aquadag of the conductive black and 1.9kg that 2, take 1.4kg respectively joins in the rear stand-by electrolytic manganese dioxide powder of baking, utilize ball mill by three kinds of dry powder blend 2h, mix complete and after waiting for dust settling, the dry powder mixed to be transferred to clean metal charging basket stand-by;
3, in a clean metallic charging basket, inject 48.5L deionized water, under the low rate mixing of mixer, the 0.8kg sodium carboxymethylcellulose taken in advance is slowly joined in deionized water, mixing speed is adjusted to fast after adding, stir 1h;
4, be dissolved in completely after deionized water forms water white transparency thick liquid until sodium carboxymethylcellulose mixing speed is adjusted to low rate mixing, the dry powder gradation mixed joins in thick liquid by materials shovel, then taking 2.4kg SBR emulsion joins in slurry, mixing speed is regulated to be quick, Keep agitation 2h, finally under negative pressure state, low rate mixing 0.5h removes bubble, and so far slurry preparation completes.
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 SBR emulsion solid content is 60%.
Preparation method is with embodiment 1.
Embodiment 3
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: 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 SBR emulsion solid content is 60%.
Preparation method is with embodiment 1.
Detect through experiment: be made into lithium manganese CR123A battery with the slurry that above-mentioned composition and engineering is prepared, in having benefited from filling a prescription, the lifting of manganese dioxide ratio and coating process are compared to the huge advantage of traditional press mold technique in precision, and test cell all possesses obvious advantage on single discharge performance or in batch cell integrated uniformity.
Claims (3)
1. be applicable to the anode sizing agent of a lithium-manganese cell of coating process, it is characterized in that lithium manganese anode sizing agent 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%; Described lithium manganese anode sizing agent is coated on aluminium foil; Described electrolytic manganese dioxide purity is 91%; Described SBR emulsion solid content is 60%.
2. the anode sizing agent being applicable to a lithium-manganese cell of coating process according to claim 1, it is characterized in that described electrolytic manganese dioxide: 45kg, conductive black: 1.4kg, aquadag 1.9kg, sodium carboxymethylcellulose: 0.8kg; SBR emulsion: 2.4kg, deionized water: 48.5L.
3. the preparation method being applicable to the anode sizing agent of a lithium-manganese cell of coating process according to above-mentioned arbitrary claim, is characterized in that it comprises the steps:
(1), take electrolytic manganese dioxide and be placed in that to be cooled to room temperature after 380 DEG C of baking ovens toast 12h stand-by;
(2), take respectively conductive black and aquadag join baking after in stand-by electrolytic manganese dioxide powder, utilize ball mill by three kinds of dry powder blend 2h, mix complete and after waiting for dust settling, the dry powder mixed to be transferred to clean metal charging basket stand-by;
(3), in a clean metallic charging basket inject deionized water, under the low rate mixing of mixer, sodium carboxymethylcellulose is slowly joined in deionized water, mixing speed is adjusted to fast after adding, stir 1h;
(4), be dissolved in completely after deionized water forms water white transparency thick liquid until sodium carboxymethylcellulose mixing speed is adjusted to low rate mixing, the dry powder gradation mixed joins in thick liquid by materials shovel, then SBR emulsion is joined in slurry, mixing speed is regulated to be quick, Keep agitation 2h, finally under negative pressure state, low rate mixing 0.5h removes bubble, and so far slurry preparation completes.
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| 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 |
| 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 |
| CN102122718A (en) * | 2011-01-24 | 2011-07-13 | 武汉昊诚能源科技有限公司 | Annular lithium and manganese battery special for external tire pressure monitoring system, and preparation method thereof |
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| JPS5676165A (en) * | 1979-11-26 | 1981-06-23 | Matsushita Electric Ind Co Ltd | Manufacture of organic-electrolyte battery |
| US20110014520A1 (en) * | 2008-07-25 | 2011-01-20 | Tomohiro Ueda | Bipolar battery |
| CN102361070A (en) * | 2011-11-08 | 2012-02-22 | 天津市泰豪锂电池有限公司 | Process for preparing positive pole of lithium battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
| CN102122718A (en) * | 2011-01-24 | 2011-07-13 | 武汉昊诚能源科技有限公司 | Annular lithium and manganese battery special for external tire pressure monitoring system, 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 |