CN103806329A - High-performance coated board paper and preparation method thereof - Google Patents
High-performance coated board paper and preparation method thereof Download PDFInfo
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Abstract
The invention provides high-performance coated board paper and a preparation method thereof. The high-performance coated board paper is prepared from an acid-resistant fiber, wherein the acid-resistant fiber is one or a mixture of more than two out of medium-alkali glass fiber, high-alkali glass fiber, ceramic fiber or polytetrafluoroethylene (PTFE) fiber according to an optional ratio. According to the coated board paper, the problems that the lead-acid cell coated board paper is low in temperature resistance, easily adhered to a polar plate, high in moisture content, high in content of Fe and Cl ions, low in acid absorption capability and different in dissolution speeds in sulfuric acid and the like are effectively solved. The coated board paper has high acid absorption and liquid retention capacity, is acid-resistant and high-temperature-resistant and is not adhered to the polar plate, cell formation is promoted, the internal resistance of the cell is effectively reduced, the content of the Fe and Cl ions is less than or equal to 30ppm, and the lead-acid cell produced by utilizing the coated board paper has excellent performances such as zero late-stage self-discharge, low internal resistance and zero difference between battery capacity and low-temperature performance.
Description
Technical field
The present invention relates to a kind of high-performance and be coated with paperboard and preparation method thereof, can be applicable to the preparation of lead-acid accumulator.
Background technology
Lead-acid accumulator is as one of important electrochmical power source, rapid in various Application Areas development, but also has in process of production the phenomenon of serious environment pollution.The grid manufacturing technique such as expanded type (drawing in the net), punching, continuous casting and rolling, for current domestic general " gravity grid casting " manufacturing technique, are " chloride plate clearer production technologies ".The flow process of this new technology is: first by " continuous casting and rolling of plumbous band " technology, lead pig is made into continuous lead band, manufacture grid by " continuous punching net (punching) technology " or " draw in the net technology " again, then through dual-side coating machine coating lead plaster, finally make lead accumulator grid.This technology is mainly cold working (except molten lead), plumbous liquid is accurately controlled at the temperature range (327-340 ℃) that approaches fusing point, then through the metal structure of quick cooling acquisition crystallization refinement, follow-up continuous pressure rolling and draw in the net, the process such as punching is all to carry out at normal temperatures, the enforcement of this technique has avoided adopting high temperature and the stirring to plumbous liquid, can not produce lead fume and lead skim, therefore block issuable lead fume discharge completely, greatly reduce energy consumption and lead loss simultaneously.
The range of application draw in the net, continuous casting connecting the continuous grid production technology such as pressure, continuous punching is increasing, and these modes account for dominant position in automobile batteries is produced.In the continuous coated plate process of these grids, generally need to adopt to be coated with paperboard, the Main Function of paper is attached to pole plate two sides while being coated plate, prevents that lead plaster from coming off and lead plaster adhesion on equipment, and prevents from when pole plate is stacking mutually adhering to each other.Have the protection of paper, in pole plate transportation, Assembling Production process, greatly reduced lead dust, be conducive to environmental protection, battery change into use procedure in paper be dissolved in electrolyte.
The material of existing painting paperboard is the common paper of string, has following shortcoming: heat resistance is poor, is prone to pole plate adhesion phenomenon in drying course; Moisture is high, and general >=6.4% reduces pole plate drying efficiency; Impurity ion content is high, and especially Fe, Cl ion concentration >=100ppm accelerates the self discharge of battery later stage, causes battery capacity decay; A little less than string is inhaled sour ability, be unfavorable in pole plate formation process sour absorption, increase the internal resistance of battery; Later stage vitriolization speed difference, paper is also partly present in polar board surface after changing into, and has increased internal resistance, has caused the difference of battery capacity and cryogenic property.
Summary of the invention
The object of this invention is to provide a kind of high-performance and be coated with paperboard and preparation method thereof.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of high-performance is coated with paperboard, is prepared from by oxytalan, and described oxytalan is the mixture of one or more any proportionings in medium-alkali glass fibre, high alkali glass fibre, ceramic fibre or PTFE fiber.
Above-mentioned painting paperboard efficiently solves in prior art that lead-acid battery is coated with that poor, the easy bonding pole plate of paperboard temperature tolerance, moisture are large, Fe, Cl ion concentration are high, inhale that sour ability is weak, the equal problem of vitriolization speed; The present invention be coated with paperboard have strong inhale sour liquid-keeping property, be conducive to battery change into, effectively reduce the internal resistance of cell, acid-resistant and anti-high-temperature, sticky pole plate, Fe, Cl ion concentration≤30ppm, that the lead-acid battery that utilizes its to produce has is little without later stage self discharge, internal resistance, the superior function of battery capacity and cryogenic property indifference.
Above-mentioned dictyosome can be polyester webs, also can be stainless steel cloth.
Described oxytalan is the mixture of medium-alkali glass fibre and high alkali glass fibre, and the filament diameter of medium-alkali glass fibre and high alkali glass fibre is 1～16 μ m, and length is 1～30mm.
Described oxytalan is that PTFE fiber and high alkali glass fibre mass ratio are the mixture of (100:0)～(30:70), and the filament diameter of PTFE fiber and high alkali glass fibre is 1～16 μ m, and length is 1～30mm.
The above-mentioned medium-alkali glass fibre (total content of alkali metal oxide Na2O and K2O is 11.9～12.4%) of selecting, the thin staple fibre of high alkali glass fibre (the total content > 12.4% of alkali metal oxide Na2O and K2O), adopt proportioning, disperse, making beating, become net, dehydration, solidify, the wet method copy paper explained hereafter glass fibre batching is coated with paperboard, by controlling solid content and starching flow and the punching slurry flow of slurry, tiltedly net (forming web, fourdrinier wire, its effect is that load glass fibre advances, be convenient to vacuum draw moisture) linear velocity (speed of a motor vehicle, be similar to oven dry, rolling speed) etc. control density and the thickness of paper.
Applicant finds after deliberation, medium-alkali glass fibre and high alkali glass fibre mix use not only can make up deficiency separately mutually, and produced unexpected cooperative effect, gained is coated with paperboard and has that intensity is high, water-tolerant, heat resistance are good, inhale acid can be strong, there is not the characteristics such as viscosity.
The filament diameter of medium-alkali glass fibre and high alkali glass fibre is all preferably 0.5～13 μ m, more preferably 1～12 μ m, and length is all preferably 2～25mm, more preferably 3～20mm.Can further guarantee to be coated with like this intensity of paperboard, promote the cooperative effect between medium-alkali glass fibre and high alkali glass fibre.
It is 0.1～0.6mm that high-performance is coated with the thick of paperboard, be preferably 0.15～0.5mm, more preferably 0.2～0.4mm, the mass ratio of medium-alkali glass fibre and high alkali glass fibre is (1:0.1)～(1:10), be preferably (1:0.5)～(1:9), more preferably (1:1)～(1:8).Can further improve like this performance that gained is coated with paperboard.
Above-mentioned high-performance is coated with the preparation method of paperboard, comprises the following steps that order is joined:
A, oxytalan is added to the water, making beating homogenizing, obtains slurry, and wherein, the quality of oxytalan and the mass ratio of water are 1:50～1:200;
B, steps A gained slurry is become to net, dries, sloughs dictyosome, rolling on dictyosome, to obtain final product, wherein, while becoming net, starching flow is 20～160L/min, and punching slurry flow is 100～900L/min.
In the prepared painting paperboard of said method, without there being bonding agent, form enough mechanical strengths by the sealed mechanism that links between fiber, resistance to elevated temperatures is good, can not bonding pole plate; So it is good that painting paperboard of the present invention has the higher acid energy of porosity suction; The lead-acid battery that the painting paperboard of manufacture of the present invention is produced has battery capacity and cryogenic property indifference, without later stage self discharge, superior function that internal resistance is little.
In above-mentioned steps B, bake out temperature is 80～270 ℃, and the time is 1～8 minute; Rolling speed is 6～50 ms/min.Can further guarantee to be coated with like this performance of paperboard.
In steps A, the quality of oxytalan and the mass ratio of water are 1:60～1:180, more preferably 1:70～1:160; In step B, while becoming net, starching flow is 30～150L/min, more preferably 40～130L/min, and punching slurry flow is 150～800L/min, more preferably 200～750L/min; Bake out temperature is 100～250 ℃, more preferably 10～240 ℃; Rolling speed is 7～40 ms/min, more preferably 8～35 ms/min.Can further guarantee to be coated with like this combination property, the especially adhesion inhibiting properties of paperboard and inhale acid.
The first-selected continuous tunnel furnace of above-mentioned drying plant and drying cylinder; Above-mentioned rolling speed is also the preparation speed that is coated with paperboard, after rolling, cuts, checks, is packaged into product.
The not specified technology of the present invention is prior art.
The present invention be coated with paperboard and there is higher porosity, have inhale sour liquid-keeping property by force, be conducive to battery change into, effectively reduce the internal resistance of cell, acid-resistant and anti-high-temperature, sticky pole plate, Fe, Cl ion concentration≤30ppm, that the lead-acid battery that utilizes its to produce has is little without later stage self discharge, internal resistance, the superior function of battery capacity and cryogenic property indifference; Preparation process of the present invention is not used any bonding agent, forms enough mechanical strengths by the sealed mechanism that links between fiber.
The specific embodiment
In order to understand better the present invention, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
In embodiment, high-performance is coated with the preparation method of paperboard, comprises the following steps that order is joined:
A, medium-alkali glass fibre and high alkali glass fibre are added to the water, making beating homogenizing, obtains slurry, wherein, the quality of medium-alkali glass fibre and high alkali glass fibre and with the mass ratio of water be 1:50～1:200;
B, by steps A gained slurry at dictyosome (28 pieces/square inch, warp thread, 26 pieces/square inch of weft yarns, mesh order number 80, be suitable for all embodiment below) on become net, dry, slough dictyosome, rolling, wherein, while becoming net, starching flow is 20～160L/min, and punching slurry flow is 100～900L/min.In embodiment, NM technology is all with reference to prior art.
Embodiment 1
The short chopping of medium-alkali glass fibre, Yancheng City Guan Da glass fibre factory product, filament diameter 6.5 μ m, length 12mm; The short chopping of high alkali glass fibre, Yutian, Hebei glass fibre Silk Mill product, filament diameter 11 μ m, length 12mm; The ratio of medium-alkali glass fibre and high alkali glass fibre is: 1:6; Glass chopped silk is 1:100 with the ratio of deionized water, upper by flow 60L/min, punching slurry flow 300L/min, and 30 meters/min of the speed of a motor vehicle, 240 ℃ of bake out temperatures, the time is 3 minutes, it is 0.3mm that gained is coated with paperboard thick.
Embodiment 2
The short chopping of medium-alkali glass fibre, Tai'an Fu Xiang fiberglass products Co., Ltd product, filament diameter 8 μ m, length 15mm; The short chopping of high alkali glass fibre, the product filament diameter 11 μ m of Yutian, Hebei glass fibre Silk Mill, length 12mm; The ratio of medium-alkali glass fibre and high alkali glass fibre is: 1:7; Glass chopped silk is 1:100 with the ratio of deionized water, upper by flow 100L/min, punching slurry flow 600L/min, and 33 meters/min of the speed of a motor vehicle, 240 ℃ of bake out temperatures, the time is 4 minutes, it is 0.2mm that gained is coated with paperboard thick.
Embodiment 3
The short chopping of medium-alkali glass fibre, Jiangxi Dahua Yuntong Fiberglass Co., Ltd.'s product, filament diameter 11 μ m, length 18mm; The short chopping of high alkali glass fibre, the product filament diameter 11 μ m of Yutian, Hebei glass fibre Silk Mill, length 12mm; The ratio of medium-alkali glass fibre and high alkali glass fibre is: 1:6; Glass chopped silk is 1:100 with the ratio of deionized water, upper by flow 60L/min, punching slurry flow 300L/min, and 30 meters/min of the speed of a motor vehicle, 240 ℃ of bake out temperatures, the time is 3 minutes, it is 0.4mm that gained is coated with paperboard thick.
Embodiment 4
The short chopping of medium-alkali glass fibre, Zigong City Changxing glass Co., Ltd product, filament diameter 7 μ m, length 20mm; The short chopping of high alkali glass fibre, the product filament diameter 11 μ m of Yutian, Hebei glass fibre Silk Mill, length 12mm; The ratio of medium-alkali glass fibre and high alkali glass fibre is: 1:7; Glass chopped silk is 1:100 with the ratio of deionized water, upper by flow 100L/min, punching slurry flow 600L/min, and 33 meters/min of the speed of a motor vehicle, 240 ℃ of bake out temperatures, the time is 5 minutes, it is 0.3mm that gained is coated with paperboard thick.
Embodiment 5
PTFE fiber, Changzhou Zhong Aoxingcheng macromolecular material Co., Ltd non-weaving cloth dedicated fiber product, diameter is 14 μ m, length 9mm; The short chopping of high alkali glass fibre, the product filament diameter 11 μ m of Yutian, Hebei glass fibre Silk Mill, length 12mm; The ratio of PTFE fiber and high alkali glass fibre is 15:85; The ratio of staple fiber and deionized water is 1:100, upper by flow 100L/min, punching slurry flow 600L/min, and 33 meters/min of the speed of a motor vehicle, 240 ℃ of bake out temperatures, the time is 4 minutes, it is 0.2mm that gained is coated with paperboard thick.
In order to contrast, the partial properties that the lead-acid battery special plant fiber (flax fibre) of Songyang County Jia Feng Science and Technology Ltd. is coated with to paperboard is chatted detection, lists in the lump in table.
In embodiment, glass is coated with the contrast table of performance and the string painting paperboard performance of paperboard
Retention of charge standard: GB/T5008.1-2005:4.4; GB/T5008.1-2005:5.7; Deposit 49 days, according to the cold-starting current discharge 30S of 0.6 times, voltage is not less than 8.0V;
Cold-starting capability standard: GB/T5008.1-2005:4.2; GB/T5008.1-2005:5.5; Under subzero 18 ℃ of environment, Is current discharge 90s, voltage >=7.5V when 10S, voltage >=7.2V when 30s, 90s voltage >=6V;
Cyclic endurance standard: GB/T19638.2-2005; 4 all after dates, cold-starting electric discharge 30S, voltage >=7.2V.
Be coated with paperboard porosity examination criteria: sampling standard is pressed GB/T6673-2001 and GB/T6672-2001,
Computing formula:
In formula:
ρ
1---the surface density of sample, unit is a gram/cm (g/cm
2);
The quality of m---sample, unit gram (g);
The length of L---sample, unit is centimetre (cm);
The width of b---sample, unit is centimetre (cm).
The porosity of p---sample, represents with %;
The thickness of d---sample, unit is centimetre (cm);
ρ
0---the density of raw material, unit is a gram/cm (g/cm
3).
Fe, Cl ion detection standard: carry out according to lead-acid battery separator examination criteria _ JB/T7603.2-2008.
Claims (10)
1. high-performance is coated with a paperboard, it is characterized in that: be prepared from by oxytalan, described oxytalan is the mixture of one or more any proportionings in medium-alkali glass fibre, high alkali glass fibre, ceramic fibre or PTFE fiber.
2. high-performance as claimed in claim 1 is coated with paperboard, it is characterized in that: described oxytalan is the mixture of medium-alkali glass fibre and high alkali glass fibre, and the filament diameter of medium-alkali glass fibre and high alkali glass fibre is 1～16 μ m, and length is 1～30mm.
3. high-performance as claimed in claim 2 is coated with paperboard, it is characterized in that: the filament diameter of medium-alkali glass fibre and high alkali glass fibre is 0.5～13 μ m, and length is 2～25mm.
4. high-performance as claimed in claim 3 is coated with paperboard, it is characterized in that: the filament diameter of medium-alkali glass fibre and high alkali glass fibre is 1～12 μ m, and length is 3～20mm.
5. the high-performance as described in claim 2-4 any one is coated with paperboard, it is characterized in that: high-performance is coated with the thick 0.1～0.6mm of being of paperboard, and the mass ratio of medium-alkali glass fibre and high alkali glass fibre is (1:0.1)～(1:10).
6. high-performance as claimed in claim 5 is coated with paperboard, it is characterized in that: high-performance is coated with the thick 0.15～0.5mm of being of paperboard, and the mass ratio of medium-alkali glass fibre and high alkali glass fibre is (1:0.5)～(1:9).
7. high-performance as claimed in claim 1 is coated with paperboard, it is characterized in that: described oxytalan is PTFE fiber and high alkali glass fibre mass ratio is the mixture of (100:0)～(30:70), the filament diameter of PTFE fiber and high alkali glass fibre is 1～16 μ m, and length is 1～30mm.
8. the high-performance described in claim 1-7 any one is coated with the preparation method of paperboard, it is characterized in that: comprise the following steps that order is joined:
A, oxytalan is added to the water, making beating homogenizing, obtains slurry, and wherein, the quality of oxytalan and the mass ratio of water are 1:50～1:200;
B, steps A gained slurry is become to net, dries, sloughs dictyosome, rolling on dictyosome, to obtain final product, wherein, while becoming net, starching flow is 20～160L/min, and punching slurry flow is 100～900L/min.
9. method as claimed in claim 8, is characterized in that: in step B, bake out temperature is 80～270 ℃, and the time is 1～8 minute; Rolling speed is 6～50 ms/min.
10. method as claimed in claim 9, is characterized in that: in steps A, the quality of oxytalan and the mass ratio of water are 1:60～1:180; In step B, while becoming net, starching flow is 30～150L/min, and punching slurry flow is 150～800L/min; Bake out temperature is 100～250 ℃; Rolling speed is 7～40 ms/min.
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Cited By (3)
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| CN112391874A (en) * | 2019-08-19 | 2021-02-23 | 桂林奇峰纸业有限公司 | Production method of coated paper for storage battery |
| CN114497759A (en) * | 2022-01-27 | 2022-05-13 | 天能电池集团（安徽）有限公司 | Coated paperboard preparation process and grid preparation method based on coated paperboard |
| CN115434184A (en) * | 2022-07-20 | 2022-12-06 | 南京玻璃纤维研究设计院有限公司 | Nano composite coated paper and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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