CN101775756B - Non-woven fabric for manufacturing Ni-MH battery sulfonated membrane, Ni-MH battery sulfonated membrane and manufacturing method thereof - Google Patents
Non-woven fabric for manufacturing Ni-MH battery sulfonated membrane, Ni-MH battery sulfonated membrane and manufacturing method thereof Download PDFInfo
- Publication number
- CN101775756B CN101775756B CN2010101245633A CN201010124563A CN101775756B CN 101775756 B CN101775756 B CN 101775756B CN 2010101245633 A CN2010101245633 A CN 2010101245633A CN 201010124563 A CN201010124563 A CN 201010124563A CN 101775756 B CN101775756 B CN 101775756B
- Authority
- CN
- China
- Prior art keywords
- sulfonation
- polypropylene
- sulfuric acid
- battery
- fibre tow
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
Abstract
The invention relates to non-woven fabric for manufacturing an Ni-MH battery sulfonated membrane, an Ni-MH battery sulfonated membrane and a manufacturing method thereof. The method comprises the following steps that: 1. hot concentrated sulfuric acid is used to singly sulfonate an ES composite filter bundle and a polypropylene fiber bundle (PP fiber bundle), and dilute sulphuric acid and water are used to clean the bundles; 2. the sulfonated fiber bundles are cut into raw material short fibers; 3. the raw material short fibers are made into a fiber mesh through a wet papermaking machine, adhered and formed into semi-finished product non-woven base material fabric by hot melting; 4. the semi-finished product non-woven base material fabric is compounded and rolled by hot melting, formed to prepare the non-woven fabric for manufacturing the Ni-MH battery sulfonated membrane by hot melting, finished and trimmed, to prepare the Ni-MH battery sulfonated membrane. From the raw material fiber bundle sulfonation to finished product manufacturing, the invention has the advantages of simple process, easy control, no large-sized equipment needed and easy industrial implementation, and solves the technical difficult problems of easy breakage and easy damage of the traditional non-woven base material fabric sulfonation.
Description
Technical field
The invention belongs to rechargeable battery diaphragm material and manufacturing technology thereof, relate to a kind of nonwoven fabric and Ni-MH battery sulfonated membrane and manufacture method thereof for making the Ni-MH battery sulfonated membrane, relate in particular to a kind of nonwoven fabric, high-capacity nickel-hydrogen battery sulfonated membrane and manufacture method thereof for making the high-capacity nickel-hydrogen battery sulfonated membrane.
Background technology
Along with the attention of countries in the world to environmental protection, Ni-MH battery has obtained fast development as free of contamination green mobile power supply.Owing to the increase to the petroleum resources consumption demand, shown out the problem that rise of the oil price and fuel-engined vehicle environmental pollution increasingly sharpen especially in recent years, developed country and the Chinese government put into effect policy, support development oil electric mixed dynamic passenger car and pure electric automobile.Japan according to the leading position, releases oil and electricity hybrid vehicle and list marketing the high-performance Ni-MH battery that its battery that adopts is exactly the high power capacity power type in this field the beginning of this century.China is better than American-European countries in the technology of the sector, serves each stadiums by the various electric vehicles of China's independent research in the 2008 Olympic Games.Current driving force type lithium battery and power-type Ni-H battery are the most competitive, are selected to oil-electric vehicle, and therefore, Development and Production high-performance power-type Ni-H battery has formed the research and development climax in battery industry.
Battery diaphragm occupies key position in battery, its effect is that the battery positive and negative electrode is separately isolated, and prevents the both positive and negative polarity contact and produces short circuit, and barrier film also need leave the electron ion path simultaneously, absorbs and reservation electrolyte.Therefore the quality of membrane properties directly affects capacity, charging/discharging voltage, self-discharge rate and the service life of battery.
In recent years, the nonwoven fabric of making take polyamide fiber as the main raw material fiber is widely used in making nickel-hydrogen battery separator after sulfonation is processed.
Understand according to the applicant, Ni-MH battery sulfonated membrane preparation method of the prior art mainly comprises following 3 steps: (1) selects first fibrous raw material, then selects suitable nonwoven forming technique to make battery diaphragm non-woven substrate cloth; (2) described battery diaphragm being carried out sulfonation modifying with non-woven substrate cloth processes; (3) the non-woven substrate cloth after the sulfonation modifying processing is carried out required post processing.
Be the preparation method that Chinese patent that CN1747199A, name are called " a kind of preparation method of nickel-hydrogen battery separator and goods thereof " relates to a kind of nickel-hydrogen battery separator such as the publication number of Tianjin University of Technology application, comprise that (1) selects the polyamide fiber that contains low density polyethylene (LDPE) is that raw material is made non-weaving cloth, and with it as the battery diaphragm base cloth; (2) process described battery diaphragm base cloth according to following technique sulfonation: sulfonating agent is that the concentrated sulfuric acid, the sulfonation temperature of 93-98% is that 129-144 ℃, sulfonation time are 10-80S, will apply to described battery diaphragm base cloth the tensile force of 10-30N/50mm simultaneously in sulfonation process; (3) sulfonation post processing: the sulfuric acid liquid through 50-70% washs 1 time successively; The sulfuric acid liquid washing of 20-30% 1 time; The pure water washed twice; Each road wash time is 3-5min; After the 80-90 ℃ of lower flatiron of oven dry 50-70min and 80-90 ℃ is smooth, can make described battery diaphragm again.
Yet there is a technical barrier that is difficult to overcome in the method for this employing non-woven substrate cloth and high-temperature concentrated sulfuric acid contact preparation sulfonated membrane always, be that non-woven substrate cloth is in high-temperature concentrated sulfuric acid sulfonation processing procedure, its intensity can significantly descend, and the non-woven substrate cloth cover produces the phenomenon of extension, breakage, fracture easily.
Originally nonwoven fabric being carried out the purpose that sulfonation processes is in order to improve the performance of barrier film, but because the existence of above-mentioned technical barrier so that the intensity of barrier film and performance the two can't take into account, apply the phenomenon that a lot of measures such as surface pressure and tensile force reduce the decline of nonwoven fabric intensity although there are many patents to adopt, but simultaneously also brought complex process, equipment investment is large, production cost is high, be unfavorable for the problem such as industrializing implementation.The more important thing is that these methods all fundamentally do not solve this long-standing technical barrier.
Summary of the invention
One of purpose of the present invention provides a kind of nonwoven fabric and Ni-MH battery sulfonated membrane of being used for making the Ni-MH battery sulfonated membrane that can satisfy the high-capacity nickel-hydrogen battery performance requirement.
Two of purpose of the present invention provides that a kind of equipment is simple, production cost is low, be easy to industrializing implementation be used for making the nonwoven fabric of Ni-MH battery sulfonated membrane and the preparation method of Ni-MH battery sulfonated membrane.This preparation method is fit to make for the nonwoven fabric of Ni-MH battery sulfonated membrane and the batch production of Ni-MH battery sulfonated membrane, and prepared Ni-MH battery sulfonated membrane can satisfy the performance requirement of high-capacity nickel-hydrogen battery, is specially adapted to high-capacity nickel-hydrogen battery.
The technical scheme that realizes the present invention's the first goal of the invention is: a kind of nonwoven fabric for making the Ni-MH battery sulfonated membrane, it is a kind of only comprising by mass fraction, the sulfonation nonwoven fabric of 40%～70% sulfonation polypropylene-polyethylene composite short fiber and 30%～60% sulfonation polypropene staple; The fiber number of described sulfonation polypropylene-polyethylene composite short fiber is 1.0dtex～1.5dtex, and the fiber number of described sulfonation polypropene staple is 0.6dtex～1.0dtex; Described sulfonation polypropylene-polyethylene composite short fiber is the composite fibre take polypropylene as inner sandwich layer, take low density polyethylene (LDPE) as exodermis.
The length of described sulfonation polypropylene-polyethylene composite short fiber is 2mm～5mm; The length of described sulfonation polypropene staple is 3mm～5mm.
Described sulfonation polypropylene-polyethylene composite short fiber is to be processed with liquid concentrated acid sulfonation separately by polypropylene-polyethylene composite fibre tow to make after the rear sulfonation polypropylene that obtains-polyethylene composite fibre tow cuts off by Len req, and described sulfonation polypropene staple is to make after the sulfonation polypropylene fibre tow of acquisition cuts off by Len req after being processed with liquid concentrated acid sulfonation separately by the polypropylene fibre tow.
Polypropylene inner sandwich layer and the low density polyethylene (LDPE) exodermis of described sulfonation polypropylene-polyethylene composite short fiber have concentric structure, and quality respectively accounts for 50%.More particularly, described sulfonation polypropylene-polyethylene composite fibre is for being the composite fibre of exodermis take melting temperature as 165 ℃ polypropylene as inner sandwich layer, take melting temperature as 129 ℃ low density polyethylene (LDPE), its polypropylene inner sandwich layer and low density polyethylene (LDPE) exodermis have concentric structure, and the two quality equates.
A kind of Ni-MH battery sulfonated membrane adopts above-mentioned nonwoven fabric for making the Ni-MH battery sulfonated membrane to make.
The technical scheme that realizes the present invention's the second goal of the invention is: a kind of preparation method of the nonwoven fabric for making the Ni-MH battery sulfonated membrane, it is to use by mass fraction, 40%～70% sulfonation polypropylene-polyethylene composite short fiber and 30%～60% sulfonation polypropene staple are through making beating, manufacture paper with pulp into net, hot melt typing, hot melt and roll typing and make the sulfonation nonwoven fabric; The fiber number of described sulfonation polypropylene-polyethylene composite short fiber is 1.0dtex～1.5dtex, and the fiber number of described sulfonation polypropene staple is 0.6dtex～1.0dtex; The preparation of described sulfonation polypropylene-polyethylene composite short fiber in turn includes the following steps:
(A1) preparation of sulfonation polypropylene-polyethylene composite fibre tow
Take polypropylene-polyethylene composite fibre tow as raw material, carry out separately making sulfonation polypropylene-polyethylene composite fibre tow after sulfonation is processed with the liquid concentrated sulfuric acid, the process for sulfonation parameter that adopts is as follows: the sulfonation time is 5min～8min, concentrated sulfuric acid temperature is 114 ℃～120 ℃, and concentrated sulfuric acid concentration is 95%～98%;
(B1) the sulfonation polypropylene that step (A1) is made-polyethylene composite fibre tow cleans up, and comprises first cleaning with dilute sulfuric acid, and then water cleans to the pH value of sulfonation polypropylene-water that the polyethylene composite fibre tow drips and is neutral;
(C1) the sulfonation polypropylene after will cleaning-polyethylene composite fibre tow is pressed Len req and is cut off, and makes sulfonation polypropylene-polyethylene composite short fiber;
The preparation of described sulfonation polypropene staple in turn includes the following steps:
(A2) preparation of sulfonation polypropylene fibre tow
Take the polypropylene fibre tow as raw material, carry out separately making sulfonation polypropylene fibre tow after sulfonation is processed with the liquid concentrated sulfuric acid, the process for sulfonation parameter that adopts is as follows: the sulfonation time is 8min～12min, and concentrated sulfuric acid temperature is 125 ℃～145 ℃, and concentrated sulfuric acid concentration is 95%～98%;
(B2) the sulfonation polypropylene fibre tow that step (A2) is made cleans up, and comprises first with dilute sulfuric acid cleaning, and then the water pH value that cleans the water that drips to sulfonation polypropylene fibre tow is neutral;
(C2) the sulfonation polypropylene fibre tow after will cleaning is pressed Len req and is cut off, and makes the sulfonation polypropene staple.
In the preparation method of above-mentioned nonwoven fabric for making the Ni-MH battery sulfonated membrane, the length of described sulfonation polypropylene-polyethylene composite short fiber is 2mm～5mm, and the length of described sulfonation polypropene staple is 3mm～5mm.
Preparation method at above-mentioned nonwoven fabric for making the Ni-MH battery sulfonated membrane, described step (B1) be sulfonation polypropylene that step (A1) is made-polyethylene composite fibre tow first with concentration be 10%～50%, temperature is that 75 ℃～90 ℃ dilute sulfuric acid cleans, and then water cleans to the pH value of sulfonation polypropylene-water that the polyethylene composite fibre tow drips and is neutral; Described step (B2) be sulfonation polypropylene fibre tow that step (A2) is made first with concentration be 10%～50%, temperature is that 75 ℃～90 ℃ dilute sulfuric acid cleans, and then the pH value that water cleans the water that drips to sulfonation polypropylene fibre tow is neutral.
More preferably, described step (B1) be sulfonation polypropylene that step (A1) is made-polyethylene composite fibre tow first with concentration be 30%～50%, temperature is that 80 ℃～90 ℃ dilute sulfuric acid cleans, and then water cleans to the pH value of sulfonation polypropylene-water that the polyethylene composite fibre tow drips and is neutral; Described step (B2) be sulfonation polypropylene fibre tow that step (A2) is made first with concentration be 30%～50%, temperature is that 80 ℃～90 ℃ dilute sulfuric acid cleans, and then the pH value that water cleans the water that drips to sulfonation polypropylene fibre tow is neutral.
More comprehensively, method is more specifically, a kind of preparation method of the nonwoven fabric for making the Ni-MH battery sulfonated membrane in turn includes the following steps:
1. the preparation of sulfonation polypropylene-polyethylene composite fibre tow and sulfonation polypropylene fibre tow
Select polypropylene-polyethylene composite fibre tow and polypropylene fibre tow as the raw fiber of the non-woven substrate cloth of making the Ni-MH battery sulfonated membrane, adopt the liquid concentrated sulfuric acid that polypropylene-polyethylene composite fibre tow and polypropylene fibre tow are carried out respectively the sulfonation processing, make sulfonation polypropylene-polyethylene composite fibre tow and sulfonation polypropylene fibre tow; The preparation of wherein said sulfonation polypropylene-polyethylene composite fibre tow may further comprise the steps successively:
(a1) polypropylene-polyethylene composite fibre tow continuous moving enters in the concentrated sulfuric acid bath, contact with the liquid concentrated sulfuric acid and to carry out sulfonation and process, the process for sulfonation parameter that adopts is as follows: the sulfonation time is 5min-8min, and concentrated sulfuric acid temperature is 114 ℃-120 ℃, and concentrated sulfuric acid concentration is 95%-98%;
(b1) the sulfonation polypropylene that obtains after being processed by concentrated acid sulfonation-polyethylene composite fibre tow continues to move in the dilute sulfuric acid rinse bath and cleans with dilute sulfuric acid, to remove the residual concentrated sulfuric acid and the sulfuric acid crystalline solid that adheres between fiber, wherein the dilute sulfuric acid temperature is 80 ℃-90 ℃, and dilute sulfuric acid concentration is 30%-50%;
(c1) the sulfonation polypropylene after dilute sulfuric acid cleans-polyethylene composite fibre tow continues to move into water cleaning in the cleaning sink, cleans to the pH value of sulfonation polypropylene-water that the polyethylene composite fibre tow drips to be neutral;
The preparation of described sulfonation polypropylene fibre tow may further comprise the steps successively:
(a2) polypropylene fibre tow continuous moving enters in the concentrated sulfuric acid bath, contact with the liquid concentrated sulfuric acid and to carry out sulfonation and process, the process for sulfonation parameter that adopts is as follows: the sulfonation time is 8min-12min, and concentrated sulfuric acid temperature is 125 ℃-145 ℃, and concentrated sulfuric acid concentration is 95%-98%;
(b2) the sulfonation polypropylene fibre tow that obtains after being processed by concentrated acid sulfonation continues to move in the dilute sulfuric acid rinse bath and cleans with dilute sulfuric acid: to remove the residual concentrated sulfuric acid and the sulfuric acid crystalline solid that adheres between fiber, wherein the dilute sulfuric acid temperature is 80 ℃-90 ℃, and dilute sulfuric acid concentration is 30%-50%;
(c2) the sulfonation polypropylene fibre tow after dilute sulfuric acid cleans continues to move into that water cleans in the cleaning sink, and the pH value that cleans the water that drips to sulfonation polypropylene fibre tow is neutral;
2. tow cutting: the sulfonation polypropylene that 1. step is made-polyethylene composite fibre tow and sulfonation polypropylene fibre tow cut off by Len req respectively, make sulfonation polypropylene-polyethylene composite short fiber and sulfonation polypropene staple;
3. net, hot melt typing are pulled an oar, manufactured paper with pulp into to batching
The sulfonation polypropylene that 2. step is made-polyethylene composite short fiber and sulfonation polypropene staple mix with water after the proportioning in proportion to be pulled an oar, dilute, disperses, and makes fibre stuff; Fibre stuff dewaters after the wet method machine of manufacturing paper with pulp is manufactured paper with pulp into fiber web, dries hot melting cohesion, cooling forming, rolling, makes semi-products Ni-MH battery sulfonated membrane non-woven substrate cloth;
4. hot melt rolls typing: with 3. prepared semi-products Ni-MH battery sulfonated membrane non-woven substrate cloth of step, individual layer or two stacked add or three layers and above stack are carried out hot melt and rolled compoundly, make for the nonwoven fabric of making the Ni-MH battery sulfonated membrane.
In the described step batching pulping process 3., the proportioning of sulfonation polypropylene-polyethylene composite short fiber and sulfonation polypropene staple is: in sulfonation staple fibre total amount, sulfonation polypropylene-polyethylene composite short fiber accounts for 40%-70%, and the sulfonation polypropene staple accounts for 30%-60%; Described sulfonation staple fibre and water mixed first making beating by weight 1: 50～1: 100, thin up is dispersed to the sulfonation staple fibre and is filament shape and partly suspending in water again after being uniformly dispersed, make fibre stuff, the final weight ratio of sulfonation staple fibre and water is 1: 1600～1: 2500.
Described step fibroreticulate oven dry sticking temperature 3. is 135 ℃～140 ℃.
Described step 4. hot melt rolls typing, the semi-products Ni-MH battery sulfonated membrane non-woven substrate cloth that 3. step is made, individual layer or two stacked add or three layers and above stack after rolling of steel rider by hot-rolling mill and rubber rollers carry out hot melt and roll compoundly, make for the nonwoven fabric of making the Ni-MH battery sulfonated membrane; The steel rider temperature of described hot-rolling mill is 140 ℃, and the temperature of the rubber rollers of described hot-rolling mill is 135 ℃.
Described step 2. after the tow cutting length of prepared sulfonation polypropylene-polyethylene composite short fiber and sulfonation polypropene staple be 2mm～5mm.Better, the described step 2. length of the rear prepared sulfonation polypropylene of tow cutting-polyethylene composite short fiber is 2mm～5mm, and the length of sulfonation polypropene staple is 3mm～5mm.
A kind of preparation method of Ni-MH battery sulfonated membrane, adopt the preparation method of above-mentioned nonwoven fabric for making the Ni-MH battery sulfonated membrane to make the nonwoven fabric of Ni-MH battery sulfonated membrane after, carry out again finish rolling and modify and make the Ni-MH battery sulfonated membrane.
Described finish rolling is modified, be that above-mentioned nonwoven fabric for making the Ni-MH battery sulfonated membrane is adopted the normal temperature finish-rolling process, adjust the gap between nip pressure and the roll, make membrane thicknesses reach designing requirement, and it is bright and clean that cloth cover is modified smooth maintenance, makes the Ni-MH battery sulfonated membrane.
The performance quality of barrier film directly depends on selection, barrier film non-woven substrate cloth braiding manufacture craft and these three committed steps of hydrophilic treatment method of barrier film nonwoven fabric manufacturing process Raw fiber.It is correct that to select raw material, suitable nonwoven forming technique be the key of manufacturing high-capacity battery barrier film non-woven substrate cloth and battery diaphragm nonwoven fabric with hydrophilic modifying technique.
The present invention selects two kinds of different fibers of polypropylene-polyethylene composite fibre (being called for short " ES composite fibre ") and polypropylene fibre (being called for short " PP fiber ") as the raw fiber of making nickel-hydrogen battery separator non-woven substrate cloth, ES composite fibre wherein, as exodermis take fusing point as 129 ℃ low density polyethylene (LDPE), take fusing point as the composite fibre of inner sandwich layer as 165 ℃ polypropylene, therefore, the ES composite fibre is called again two component low melting point heat-fusible composite fibers.In non-woven substrate cloth manufacturing process, the exodermis low density polyethylene (LDPE) of ES composite fibre plays the hot melting cohesion effect.But because the ES composite fibre is the composite fibre with skin-core structure, its fiber number is relatively thick, and general fiber number is more than 1.0dtex; When being lower than 1.0dtex, the low density polyethylene (LDPE) on fiber top layer easily breaks.And the excessive membrane pore size that can cause of the fiber number of fiber is excessive, causes easily battery short circuit, thus also must cooperate the thinner PP fiber of fiber number, to satisfy the requirement of high-capacity nickel-hydrogen battery barrier film porous microcellular structure.
The PP fiber, i.e. polypropylene fibre, its fusing point is 165 ℃, and chemical stability is good, and fiber number is thin, and the effect in non-woven substrate cloth manufacturing process is the fiber micropore that forms high density, porous, prevents that battery from producing short circuit.In the present invention, consider the cost of raw fiber and being easy to get property, having adopted fiber number is the PP fiber of 0.6dtex-1.0dtex.
Because the ES composite fibre is different with the melting temperature of PP fiber, performance is different, and role is not identical yet in non-woven substrate cloth manufacturing process, if according to existing barrier film preparation method, namely make first non-woven substrate cloth, and then carry out sulfonation and process, then since two kinds of different fibers can't take into account at sulfonation temperature with on the sulfonation time, thereby in high-temperature concentrated sulfuric acid sulfonation processing procedure, will inevitably greatly reduce the intensity of non-woven substrate cloth.Even adopt simultaneously and apply remedial measure or the equipment such as surface pressure and tensile force, can not solve fundamentally that non-woven substrate cloth intensity in high-temperature concentrated sulfuric acid sulfonation processing procedure obviously descends, the nonwoven cloth cover produce extend, damaged, fracture phenomenon.
The present invention is with ES composite fibre and the PP fiber raw fiber as barrier film non-woven substrate cloth, and carrying out separately first sulfonation processes, and then cut into staple fibre and make Ni-MH battery sulfonated membrane nonwoven fabric through the wet method papermaking process, and further make the Ni-MH battery sulfonated membrane.This preparation method compares with existing preparation method, technological process science, reasonable, and also equipment is simple, easily operation, is conducive to industrializing implementation.The ES composite fibre with the tow form in 114 ℃-120 ℃ high-temperature concentrated sulfuric acid, tighten by, the low density polyethylene (LDPE) on its fiber top layer and the sulfur trioxide generation sulfonating reaction in the high-temperature concentrated sulfuric acid, and the polypropylene of its fiber inner sandwich layer does not reach reaction temperature, and fibre strength can not descend; In the sulfonation processing procedure, even produce the pulling force of every bundle 80kg when the ES composite fibre filament is pulled roll traction walking, the ES composite fibre filament can fracture yet.And the top layer low density polyethylene (LDPE) of ES composite fibre filament does not also reach softening point, can not stick together between fiber yet, the ES composite fibre filament still can keep good dispersiveness after cut-out, thereby can greatly improve the Performance and quality of nickel-hydrogen battery separator non-woven substrate cloth and nonwoven fabric.The PP fiber passes through in 125 ℃-145 ℃ high-temperature concentrated sulfuric acid with the tow form; When this temperature, the sulfur trioxide in the concentrated sulfuric acid and the aggravation of PP fiber-reactive, PP fiber sulfonation time course is accelerated, thereby can finish the sulfonation processing of PP fiber (polypropylene fibre) within than the faster time (about 10min).
It also is one of necessary links of processing of sulfonation that the ES composite fibre filament that sulfonation is processed and polypropylene fibre tow clean.To carry out ES composite fibre filament and the directly water cleaning of polypropylene fibre tow after sulfonation is processed with high-temperature concentrated sulfuric acid, because sulfonation ES composite fibre filament and sulfonation polypropylene fibre tow are at this moment all with a large amount of high-temperature high concentration sulfuric acid, as directly entering in the water, meet water vigorous reaction namely occurs, at this moment the high temperature of moment generation can be with fiber fusing or charing, so the present invention elder generation working concentration is 10%-50%, temperature remains on 75 ℃-90 ℃ dilute sulfuric acid cleaning as transition, being more preferably and selecting concentration is 30%-50%, temperature remains on 80 ℃-90 ℃ dilute sulfuric acid cleaning as transition, and preferably selecting concentration is 30%-50%, temperature remains on 85 ℃-90 ℃ dilute sulfuric acid cleaning as transition.When cleaning with dilute sulfuric acid, also can heat to dilute sulfuric acid, as long as continue in proportion to add entry, mix the reaction temperature that produces required dilute sulfuric acid temperature and concentration can keep cleaning the time with the concentrated sulfuric acid that fibre bundle is brought into.
The present invention's prepared Ni-MH battery sulfonated membrane nonwoven fabric and barrier film thereof can satisfy the performance requirement of high-capacity nickel-hydrogen battery, are specially adapted to high-capacity nickel-hydrogen battery.
Technique effect of the present invention
The present invention selects ES composite fibre and PP fiber as the raw fiber of nickel-hydrogen battery separator nonwoven fabric, and two kinds of raw fibers will making the barrier film nonwoven fabric carry out respectively first the concentrated acid sulfonation modification, be that the ES composite fibre filament is implemented separately sulfonation with not identical sulfonation temperature, sulfonation time respectively with the PP fibre bundle, and then cut into respectively staple fibre, adopt the wet method papermaking process to make semi-products Ni-MH battery sulfonated membrane non-woven substrate cloth, and then make for nonwoven fabric and the Ni-MH battery sulfonated membrane of making the Ni-MH battery sulfonated membrane.
The nonwoven fabric that is used for making Ni-MH battery sulfonated membrane that the present invention obtains and Ni-MH battery sulfonated membrane are because sulfonation ES composite short fiber and the sulfonation PP staple fibre of selecting in advance sulfonation to process are raw material, thereby need not the finished product nonwoven fabric is carried out the sulfonation processing again, thereby fundamentally avoided non-woven substrate cloth intensity in high-temperature concentrated sulfuric acid sulfonation processing procedure significantly to descend, the nonwoven cloth cover produces and extends, damaged, the phenomenon of fracture, therefore, the nonwoven fabric that obtains and sulfonated membrane quality are high, stable performance, and raw material is easy to get, cost is low, is specially adapted to high-capacity nickel-hydrogen battery.
Because the present invention carries out in advance sulfonation treatment process to the raw fiber that is used for the making nonwoven fabric, rather than nonwoven fabric carried out sulfonation, changed irrational technological process among the existing preparation method, therefore, the present invention can effectively avoid non-woven substrate cloth intensity in high-temperature concentrated sulfuric acid sulfonation processing procedure significantly to descend, the nonwoven cloth cover produces and extends, damaged, the phenomenon of fracture, fundamentally overcome the contradiction that prior art can't be taken into account at the fiber process for sulfonation not of the same race that the non-woven substrate cloth that is made of the plurality of raw materials fiber is carried out produce when sulfonation is processed, solved the in the past long-standing technical barrier of non-woven substrate cloth sulfonation treatment process, it is simple obviously to have method, flow process is reasonable, the advantage of science.
Secondly, the present invention compared with prior art, do not need special surface pressure or the tensile force of applying preventing measure and the equipment of nonwoven fabric strength decreased in sulfonation process, so have also that equipment is simple, production cost is low, an advantage of easy operating and industrializing implementation.
Because whole technological process of the present invention is scientific and reasonable, production technology has preferably continuity, and therefore, production efficiency also improves greatly, is applicable to produce in enormous quantities; Prepared nonwoven fabric and Ni-MH battery sulfonated membrane output for making the Ni-MH battery sulfonated membrane is high, and cost is low, and stable performance; Prepared Ni-MH battery sulfonated membrane nonwoven fabric and Ni-MH battery sulfonated membrane are specially adapted to high-capacity nickel-hydrogen battery.
Description of drawings
Fig. 1 is the schematic diagram of sulfonation treating apparatus of the present invention;
Fig. 2 be the present invention adopt be the ES complex structure of filament cutaway view of inner sandwich layer take fusing point as 129 ℃ low density polyethylene (LDPE) as exodermis, take fusing point as 165 ℃ polypropylene.
The specific embodiment
Below in conjunction with concrete operating procedure and embodiment the present invention is further described in detail, but is not limited to this.Used various raw materials among the embodiment unless otherwise indicated, are commercially available industrial goods; Used ES composite fibre filament and polypropylene fibre tow are to the long fiber boundling silk of chemical fibre factory buying (do not do after the tow spinning to cut off and process), tow length about 2000 meters～3000 meters (length can be decided as required), the place of production is Yancheng, Jiangsu Province; The fiber number of ES composite fibre wherein is between 1.0dtex～1.5dtex; The ES composite fibre is to be the composite fibre of inner sandwich layer take fusing point as 129 ℃ low density polyethylene (LDPE) as exodermis, take fusing point as 165 ℃ polypropylene, the low density polyethylene (LDPE) that is positioned at exodermis respectively accounts for 50% (mass percent) with the polypropylene that is positioned at inner sandwich layer, and be concentric distribution, as shown in Figure 2, wherein label 1 indication is the low density polyethylene (LDPE) that is positioned at exodermis, and what label 2 was indicated is the polypropylene that is positioned at inner sandwich layer; The fiber number of polypropylene fibre (PP fiber) is between 0.6dtex～1.0dtex; Used tow cutting machine is domestic, Zhejiang, the place of production; The used machine of manufacturing paper with pulp is the oblique net of the homemade wet method machine of manufacturing paper with pulp; Used hot-rolling mill is domestic, Jiangsu, the place of production; The sulfonation treating apparatus is self-control, and the schematic diagram of sulfonation treating apparatus as shown in Figure 1.
The sulfonation treating apparatus divides four parts, is comprised of concentrated sulfuric acid bath, dilute sulfuric acid bath and 2 cleaning sinks.First is concentrated sulfuric acid bath, material is the resistant materials such as the stainless steel of the high temperature resistant concentrated sulfuric acid or enamel, also can be take other materials as core, outer surface coats the combined material of enamel, can be rectangle, also can be other suitable shapes, as shown in Figure 1, in concentrated sulfuric acid bath inside and two ends 6 stainless steel deflector rolls have been installed altogether, wherein have in 4 high-temperature concentrated sulfuric acid liquid that can be immersed in the concentrated sulfuric acid bath; Mode of heating can be the external heat of thermal source for using natural gas or liquefied gas, also can adopt other suitable thermals source;
Second portion is the dilute sulfuric acid bath, and material is PP plastic plate or other suitable materials, and the two ends of dilute sulfuric acid bath and inside are equipped with 4 polytetrafluoroethylene (PTFE) deflector rolls altogether, wherein has 2 can be immersed in the dilute sulfuric acid liquid; Be provided with in addition 2 dilute sulfuric acid showers above the dilute sulfuric acid bath, and use acidproof circulating pump to realize the circulation of dilute sulfuric acid in bath, the quantity of polytetrafluoroethylene (PTFE) deflector roll and dilute sulfuric acid shower can arrange according to need of production.
Three, the 4th one is respectively cleaning sink.Cleaning sink also can only be established more than 1 or 2.The water that fills in the cleaning sink is for being preferably circulating water.
The first Traction Drive roll is being installed to the second Traction Drive roll pair is installed between, the third and fourth part between first and the second portion.The second Traction Drive roll to also can be installed in second and third part between.The installation quantity that the Traction Drive roll is right and position all can be adjusted according to producing actual needs.In addition, the quantity of the polytetrafluoroethylene (PTFE) deflector roll of the quantity of the stainless steel deflector roll of concentrated sulfuric acid bath internal placement and dilute sulfuric acid bath internal placement also can be adjusted according to the needs of actual production.
As shown in Figure 1,1 is the fibre bundle conveying roller; 2,3,4,5,6,7 is the stainless steel deflector roll, and 8 and 9 is the first Traction Drive roll pair, and 18 and 19 is the second Traction Drive roll pair, and 10,11,12,13 is the polytetrafluoroethylene (PTFE) deflector roll, and 14,15,16,17,20,21,22,23 is the stainless steel deflector roll; 24 are fibre bundle output rod; 25,26 is the dilute sulfuric acid shower; 27 indicated be fibre bundle; 28 indicated be the concentrated sulfuric acid in the concentrated sulfuric acid bath; 29 indicated be dilute sulfuric acid in the dilute sulfuric acid bath; 30 indicated be water in the cleaning sink; Need to prove, in Fig. 1, omitted some common equipments such as used concentrated sulfuric acid circulating pump, dilute sulfuric acid circulating pump, water pump in the sulfonation treating apparatus.
Concrete operating procedure is:
1. the preparation of sulfonation polypropylene-polyethylene composite fibre tow (sulfonation ES composite fibre filament)
Get ES composite fibre filament 2-3 bundle (about 100,000 monofilament) and penetrate in the high-temperature concentrated sulfuric acid bath and on deflector roll, back and forth pass, then pass successively the first Traction Drive roll to (8,9), dilute sulfuric acid bath, the first cleaning sink, the second Traction Drive roll to (18,19), the second cleaning sink.Add the concentrated sulfuric acid in the concentrated sulfuric acid bath and be used for submergence ES composite fibre filament, concentrated sulfuric acid concentration is 95%-98%, is warming up to 114 ℃-120 ℃, and the dilute sulfuric acid bath adds dilute sulfuric acid, and concentration is 10%-50%, and reaction temperature remains on 75 ℃-90 ℃; Be more preferably in the dilute sulfuric acid bath that to add concentration be the dilute sulfuric acid of 30%-50%, reaction temperature remains on 80 ℃-90 ℃ or 85 ℃-90 ℃.Add running water in the cleaning sink, open Traction Drive roll pair, the ES composite fibre filament passes through in concentrated sulfuric acid groove, dilute sulfuric acid tank, cleaning sink successively in order synchronously, the sulfonation time about 5min-8min of ES composite fibre filament in high-temperature concentrated sulfuric acid, opening simultaneously dilute sulfuric acid circulating pump, water pump dilutes, washes the ES composite fibre filament after the sulfonation respectively, clean residual sulfuric acid, make ES composite fibre filament flushing to the pH value of its water that drips be neutral, make sulfonation ES composite fibre filament.
2. the preparation of sulfonation polypropylene fibre tow (sulfonation PP fibre bundle)
1. the polypropylene fibre tow is carried out sulfonation by step and process, but adopt different sulfonation processing and dilute sulfuric acid cleaning: concentrated sulfuric acid concentration is 95%-98%, and concentrated sulfuric acid temperature is 125 ℃-145 ℃, about 8min-12min of sulfonation time; Dilute sulfuric acid concentration is 10%-50%, and the dilute sulfuric acid temperature is 75 ℃-90 ℃; Better can select concentration is the dilute sulfuric acid of 30%-50%, and the dilute sulfuric acid temperature is 80 ℃-90 ℃ or 85 ℃-90 ℃, makes sulfonation polypropylene fibre tow (sulfonation PP fibre bundle).
3. tow cutting; The sulfonation that will 1. make by step with the tow cutting machine is processed, moisture content is sulfonation ES composite fibre filament 3-5 bundle (ten thousand of the about 30-50) cut-out under the moisture state of 30%-40%, makes length and be the sulfonation polypropylene of 2mm-5mm-polyethylene composite short fiber; With the sulfonation polypropylene filaments tractotomy that 2. step makes, making length is the sulfonation polypropene staple of 3mm-5mm with the tow cutting machine.
4. net, hot melt typing are pulled an oar, manufactured paper with pulp into to batching
The sulfonation polypropylene that 3. step is made-polyethylene composite short fiber, sulfonation polypropene staple weigh by required prescription mix making beating in an amount of water of rear input, thin up is dispersed to the raw material staple fibre and is the filament shape and partly suspends in water again, makes fibre stuff; Fibre stuff is manufactured paper with pulp into fiber web through the wet method machine of manufacturing paper with pulp, and through dehydration, oven dry hot melting cohesion, cooling forming, rolling, makes semi-products Ni-MH battery sulfonated membrane non-woven substrate cloth again.
5. hot melt, compound, roll
The semi-products Ni-MH battery sulfonated membrane non-woven substrate cloth that 4. step is made, individual layer or double-deck or three layers and above stack, by steel rider and the rubber rollers of two roller hot-rolling mills, carry out hot melt, compound, roll, make for the nonwoven fabric of making the Ni-MH battery sulfonated membrane.
6. finish rolling is modified
The nonwoven fabric that is used for making Ni-MH battery sulfonated membrane that 5. step is made adopts the normal temperature finish-rolling process, adjust the gap between nip pressure and the adjusting roll, make membrane thicknesses reach designing requirement, and it is bright and clean that cloth cover is modified smooth maintenance, makes the Ni-MH battery sulfonated membrane.
The prescription of the raw material staple fibre that 4. described step adopts is as follows: in raw material staple fibre total amount, sulfonation polypropylene-polyethylene composite short fiber accounts for 40%-70%, and the sulfonation polypropene staple accounts for 30%-60%; The fiber beating consistency that 4. described step adopts is: fiber is 1: 50～1: 100 with the initial weight ratio of water; After disperseing dilution, further add water and stir, fiber is disperseed fully, fiber is 1: 1600～1: 2500 with the final weight ratio of water in the fibre stuff.In 4. step prepared burden pulping process, the weight of the raw material staple fibre that takes by weighing referred to the weight of removing behind the fiber contained humidity.
4. described step dries hot melting cohesion through the wet method machine of the manufacturing paper with pulp fiber web that makes of manufacturing paper with pulp in baking oven, the oven dry sticking temperature is 135 ℃-140 ℃, in order to make wherein low-melting fiber and dystectic fiber generation hot melting cohesion;
5. described step carries out to semi-products Ni-MH battery sulfonated membrane non-woven substrate cloth that hot melt is compound to roll, and the steel rider temperature of described hot-rolling mill is 140 ℃, and the temperature of rubber rollers is 135 ℃; And apply the thickness that suitable pressure is controlled nonwoven fabric, reserve diaphragm design thickness+0.02mm, so that the finish rolling modification process of back.
The method for preparing Ni-MH battery sulfonated membrane nonwoven fabric and Ni-MH battery sulfonated membrane is as follows:
1. the preparation of sulfonation polypropylene-polyethylene composite fibre tow (sulfonation ES composite fibre filament)
ES composite fibre filament 2～3 bundles of getting fiber number and be 1.5dtex are merged (about 100,000 monofilament) by the stainless steel deflector roll 2 of concentrated sulfuric acid bath input, penetrate in the concentrated sulfuric acid bath, and at the stainless steel deflector roll (3 of concentrated sulfuric acid bath inside, 4,5,6) back and forth pass on for several times, making the ES composite fibre filament is 30 meters through length back and forth in concentrated sulfuric acid bath, then continues the stainless steel deflector roll 7 through concentrated sulfuric acid bath output, first pair of Traction Drive roll is to (8,9) guiding penetrates the dilute sulfuric acid bath, the first cleaning sink, the second Traction Drive roll is to (18,19), the second cleaning sink; The running water that adds respectively normal temperature in the concentrated sulfuric acid bath in the concentrated sulfuric acid of adding concentration 98%, the dilute sulfuric acid bath in the dilute sulfuric acid of adding concentration 35%, the first cleaning sink, the second cleaning sink.The concentrated sulfuric acid is warming up to 118 ℃, and the temperature of dilute sulfuric acid is 90 ℃; Open two traction milling trains, linear speed is adjusted to 4 meters of per minutes, and the ES composite fibre filament continues 7.5 minutes in the concentrated sulfuric acid, open simultaneously concentrated sulfuric acid circulating pump, makes the high-temperature concentrated sulfuric acid temperature in the bath even; Open dilute sulfuric acid pump to the sulfonation ES composite fibre filament flushing through dilute sulfuric acid tank, remove the concentrated sulfuric acid raffinate and the sulfuric acid crystalline solid that adhere between the fiber; Open water service pump to the sulfonation ES composite fibre filament flushing through cleaning sink, the pH value that always washes the water that drips to sulfonation ES composite fibre filament is neutral.
Other gets fiber number is that ES composite fibre filament 2～3 bundle of 1.0dtex is merged (about 100,000 monofilament) and carries out sulfonation by above-mentioned same method and process.
2. the preparation of sulfonation polypropylene fibre tow (sulfonation PP fibre bundle)
The polypropylene fibre tow that with fiber number is 0.7dtex prepares sulfonation polypropylene fibre tow (sulfonation PP fibre bundle) by step method 1., but the sulfonation that it adopts and dilute sulfuric acid cleaning all are different from the ES composite fibre filament: the concentration of the concentrated sulfuric acid is 95%, concentrated sulfuric acid temperature is 140 ℃, and the duration of polypropylene fibre tow in concentrated sulfuric acid groove is 10min; The concentration of dilute sulfuric acid is 30%, and the temperature of dilute sulfuric acid is 85 ℃.
3. tow cutting
1.5dtex after sulfonation processed and the sulfonation ES composite fibre filament of 1.0dtex are cut to respectively the length of 2mm～5mm with the tow cutting machine under moisture state, making uses the same method is cut to the sulfonation polypropylene fibre tow of the 0.7dtex after the sulfonation processing length of 3mm～5mm under moisture state.
4. net, hot melt typing are pulled an oar, manufactured paper with pulp into to batching
Take by weighing the sulfonation polypropylene of raw material staple fibre: 0.8kg-polyethylene composite short fiber (fiber number 1.5dtex, length 5mm) by following proportioning and account for 10%; 1.6kg sulfonation polypropylene-polyethylene composite short fiber (fiber number 1.0dtex, length 3mm), account for 20%; 2.4kg sulfonation polypropylene-polyethylene composite short fiber (fiber number 1.0dtex, length 2mm), account for 30%; 3.2kg sulfonation polypropene staple (fiber number 0.7dtex, length 3mm), account for 40%; The weight of the raw material staple fibre that wherein takes by weighing refers to the weight of removing behind the fiber contained humidity.
With the sulfonation polypropylene that taken by weighing-polyethylene composite short fiber and sulfonation polypropene staple with put into storage slurry cylinder after water mixed making beating by 1: 50, thin up is dispersed to the raw material staple fibre and is filament shape and partly suspending in water, make fibre stuff, the ratio of its fiber and water is 0.4: 1000.
With the oblique net of the wet method machine of manufacturing paper with pulp the above-mentioned fibre stuff that makes is introduced flow controller through water pump, the control constant flow, the flow box online of the machine of manufacturing paper with pulp of flowing through through vacuum draw, is removed fiber web moisture;
Fiber web after the dehydration enters the plain net baking oven of the machine of manufacturing paper with pulp, and the oven dry sticking temperature in the baking oven is 135 ℃.
The exodermis low density polyethylene (LDPE) of the sulfonation polypropylene in the fiber web-polyethylene composite short fiber is subjected to be fused into the semifluid shape after the temperature, fiber and fiber intersection points produce bonding point, fiber web produces adhesion strength after going out the baking oven cooling, last rolling makes semi-products Ni-MH battery sulfonated membrane non-woven substrate cloth, and individual layer weight is 21g/m2.
5. hot melt, compound, roll
The semi-products Ni-MH battery sulfonated membrane non-woven substrate cloth that 4. step is made adopted for three stacked adding, by two roller hot-rolling mills, 140 ℃ of its steel roller faces temperature, the exodermis low density polyethylene (LDPE) of the ES composite fibre that contains in the non-woven substrate cloth when semi-products Ni-MH battery sulfonated membrane non-woven substrate cloth contacts with steel roller faces melts again, elastic silicone rubber roller in the hot-rolling mill is controlled the fluidity of molten that has melted, and keeps the gas permeability of non-woven substrate cloth.Simultaneously non-woven substrate cloth is exerted pressure and roll, regulate base material thickness, further the bonding point contact-making surface between reinforcing fibre significantly increases the rear intensity of non-woven substrate cloth cooling; Last rolling makes for the nonwoven fabric of making the Ni-MH battery sulfonated membrane.
6. finish rolling is modified
The nonwoven fabric that be used for to make the Ni-MH battery sulfonated membrane that 5. step is made carries out finish rolling and modification makes the Ni-MH battery sulfonated membrane through two-roller mill; The roll of described two-roller mill is steel rider, and temperature is normal temperature; Adjust nip pressure and regulate gap between the roll, make membrane thicknesses reach designing requirement, and it is bright and clean that cloth cover is modified smooth maintenance.
Above-mentioned prepared nonwoven fabric and Ni-MH battery sulfonated membrane for making the Ni-MH battery sulfonated membrane is specially adapted to high-capacity nickel-hydrogen battery.
The method for preparing Ni-MH battery sulfonated membrane nonwoven fabric and Ni-MH battery sulfonated membrane is as follows:
1. the preparation of sulfonation polypropylene-polyethylene composite fibre tow (sulfonation ES composite fibre filament)
By the step among the embodiment 1 1. method prepare sulfonation polypropylene fibre tow (sulfonation PP fibre bundle), but the process for sulfonation that adopts and dilute sulfuric acid cleaning are different: the concentration of the concentrated sulfuric acid is 96%, and concentrated sulfuric acid temperature is 120 ℃, and the retention time is 6min; The concentration of dilute sulfuric acid is 50%, and the temperature of dilute sulfuric acid is 90 ℃;
2. the preparation of sulfonation polypropylene fibre tow (sulfonation PP fibre bundle)
By the step among the embodiment 1 1. method prepare sulfonation polypropylene fibre tow (sulfonation PP fibre bundle), but the process for sulfonation that adopts and dilute sulfuric acid cleaning are different: the concentration 98% of the concentrated sulfuric acid, concentrated sulfuric acid temperature are 142 ℃, and the retention time is 8min; The concentration of dilute sulfuric acid is 50%, and the dilute sulfuric acid temperature is 90 ℃;
3. tow cutting: sulfonation ES composite fibre filament, sulfonation polypropylene fibre tow are cut to respectively 2-4mm length with the fibre bundle cutting machine;
4. net, hot melt typing are pulled an oar, manufactured paper with pulp into to batching
Take by weighing the sulfonation polypropylene of raw material staple fibre: 0.4kg-polyethylene composite short fiber (fiber number 1.5dtex, length 4mm) by following proportioning, account for 5%; 1.6kg sulfonation polypropylene-polyethylene composite short fiber (fiber number 1.0dtex, length 3mm), account for 20%; The sulfonation polypropylene of 2kg-polyethylene composite short fiber (fiber number 1.0dtex, length 2mm) accounts for 25%; The sulfonation polypropene staple of 4kg (fiber number 0.8dtex, length 3mm) accounts for 50%; The weight of the raw material staple fibre that wherein takes by weighing refers to the weight of removing behind the fiber contained humidity.
With the above-mentioned raw material staple fibre that takes by weighing by embodiment 1 step 4. method mix making beating, manufacture paper with pulp, the hot melt typing, make semi-products Ni-MH battery sulfonated membrane non-woven substrate cloth, individual layer weight is 28g/m2;
5. hot melt, compound, roll
Two stacked the adding of semi-products Ni-MH battery sulfonated membrane non-woven substrate cloth that 4. step is made, by two roller hot-rolling mills, 140 ℃ of its steel roller faces temperature, the exodermis low density polyethylene (LDPE) of the ES composite fibre that contains in the non-woven substrate cloth when non-woven substrate cloth contacts with steel roller faces melts again, elastic silicone rubber roller in the hot-rolling mill is controlled the fluidity of molten that has melted, and keeps the gas permeability of non-woven substrate cloth; Simultaneously non-woven substrate cloth is exerted pressure and roll, regulate base material thickness, further the bonding point contact-making surface between reinforcing fibre significantly increases the rear intensity of non-woven substrate cloth cooling; Last rolling makes for the nonwoven fabric of making the Ni-MH battery sulfonated membrane;
6. finish rolling is modified
The nonwoven fabric that is used for making Ni-MH battery sulfonated membrane that 5. step is made makes the Ni-MH battery sulfonated membrane after two-roller mill carries out finish rolling and modifies; The roll of wherein said two-roller mill is steel rider, and temperature is normal temperature, adjusts nip pressure and regulates gap between the roll, makes membrane thicknesses reach designing requirement, and it is bright and clean that cloth cover is modified smooth maintenance.
Above-described embodiment 2 prepared nonwoven fabric and Ni-MH battery sulfonated membranes for making the Ni-MH battery sulfonated membrane are specially adapted to high-capacity nickel-hydrogen battery.
Embodiment 3
The method for preparing Ni-MH battery sulfonated membrane nonwoven fabric and Ni-MH battery sulfonated membrane is as follows:
1. the preparation of sulfonation polypropylene-polyethylene composite fibre tow (sulfonation ES composite fibre filament)
By embodiment 1 step 1. method process, but the process for sulfonation that adopts and dilute sulfuric acid cleaning are different: concentrated sulfuric acid concentration 95%, 116 ℃ of concentrated sulfuric acid temperature, retention time 8min; Dilute sulfuric acid concentration 30%, 80 ℃ of dilute sulfuric acid temperature;
2. the preparation of sulfonation polypropylene fibre tow (sulfonation PP fibre bundle)
By embodiment 1 step 1. method process, but the process for sulfonation that adopts and dilute sulfuric acid cleaning are different: concentrated sulfuric acid concentration 96%, 135 ℃ of temperature, retention time 10min; Dilute sulfuric acid concentration 40%, 85 ℃ of temperature;
3. tow cutting: 3. carry out the tow cutting by embodiment 2 steps;
4. net, hot melt typing are pulled an oar, manufactured paper with pulp into to batching
Take by weighing the sulfonation polypropylene of raw material staple fibre: 3kg-polyethylene composite short fiber (fiber number 1.0dtex, length 3mm) by following proportioning, account for 25%; 3.6kg sulfonation polypropylene-polyethylene composite short fiber (fiber number 1.0dtex, length 2mm), account for 30%; The sulfonation polypropene staple of 3kg (fiber number 1.0dtex, length 4mm) accounts for 25%; The sulfonation polypropene staple of 2kg (fiber number 0.7dtex, length 3mm) accounts for 20%; The weight of the raw material staple fibre that wherein takes by weighing refers to the weight of removing behind the fiber contained humidity.
After the above-mentioned raw material staple fibre that has taken by weighing and water mixed making beating by 1: 100, put into storage slurry cylinder, thin up is dispersed to the raw material staple fibre and is the filament shape and partly suspends in water, and in the prepared fibre stuff, the final ratio of fiber and water is 1: 1666; By embodiment 1 step 4. method manufacture paper with pulp, hot melt typing, make semi-products Ni-MH battery sulfonated membrane non-woven substrate cloth, individual layer weight is 50g/m2;
5. hot melt, compound, roll
The semi-products Ni-MH battery sulfonated membrane non-woven substrate cloth that 4. step is made, individual layer is by two roller hot-rolling mills, 138 ℃ of its steel roller faces temperature, the exodermis low density polyethylene (LDPE) of the ES composite fibre that contains in the non-woven substrate cloth when non-woven substrate cloth contacts with steel roller faces is melted by temperature again, elastic silicone rubber roller in the milling train is controlled the flowability of the melt that melted, guarantees the gas permeability of non-woven substrate cloth; Simultaneously non-woven substrate cloth is pressurizeed and roll, regulate base material thickness, further the bonding point contact-making surface between reinforcing fibre significantly increases the rear intensity of non-woven substrate cloth cooling, and last rolling makes for the nonwoven fabric of making the Ni-MH battery sulfonated membrane;
6. finish rolling is modified
The nonwoven fabric that is used for making Ni-MH battery sulfonated membrane that uses two roller finishing mills that 5. step is made carries out the finish rolling modification and makes the Ni-MH battery sulfonated membrane; The roll of wherein said two roller finishing mills is steel rider, and temperature is normal temperature; Adjust nip pressure and regulate gap between the roll, make sulfonated membrane thickness reach designing requirement, it is bright and clean simultaneously cloth cover to be modified smooth maintenance.
Above-described embodiment 3 prepared nonwoven fabric and Ni-MH battery sulfonated membranes for making the Ni-MH battery sulfonated membrane are specially adapted to high-capacity nickel-hydrogen battery.
The part of not describing in detail in above-described embodiment 1～3 can foregoing with reference to the present invention " concrete operating procedure ", and other NM technique can be with reference to grafted polypropylene diaphragm and the manufacture method (patent No. is ZL200610088413.5) thereof before the applicant.
Characteristics of the present invention are that the raw fiber tow is carried out sulfonation in advance to be processed, and then carry out the production of nickel-hydrogen battery separator non-woven substrate cloth and nonwoven fabric, manufacturing process flow rationally, science, fundamentally solved the technical barrier that cloth cover breakage, fracture appear in non-woven substrate cloth when making first barrier film non-woven substrate cloth in the past and carrying out sulfonation again and process; Manufacture method of the present invention is simple simultaneously, need not special installation, and equipment investment is less; The production technology continuity is good, and production efficiency improves greatly, and the output of product is high, and cost is low, and end product quality is stable, has good market prospects.
The individual layer weight of the prepared semi-products Ni-MH battery of the present invention sulfonated membrane non-woven substrate cloth is measured by SJ/T10171.1～10171.12-91 standard.
With the embodiment of the invention 2 prepared barrier films and Japan FV4365K and Germany these 2 kinds barrier films that abroad use for nickel-hydrogen battery of FS2226-14 all be the battery of AAA650 for battery size, and carry out the contrast test of a series of battery performances, the every test result that obtains sees Table 1～table 4.
(1) battery capacity and internal resistance detection are relatively
Table 1 battery capacity and internal resistance detection
Can learn relatively that from the data of table 12 kinds of barrier films of the embodiment of the invention 2 prepared barrier films and other are compared, the performance of each side all is best.
(2) performance test of overcharging
Respectively get 5 experimental cells, 1C charging 90 minutes, the result is as shown in table 2.
Table 2 performance test of overcharging
| |
2 | 4 | 6 | 8 | 10 |
| The N/P value | 1.213 | 1.182 | 1.181 | 1.185 | 1.181 |
| The time of losing heart | - | - | - | - | - |
| The leakage time | - | - | - | - | - |
| FS2226-14 | 35 | 39 | 40 | 41 | 50 |
| The N/P value | 1.238 | 1.217 | 1.210 | 1.226 | 1.172 |
| The time of losing heart | - | - | - | - | - |
| The leakage time | - | - | 81min | - | - |
| Barrier film of the present invention | 52 | 59 | 67 | 71 | 75 |
| The N/P value | 1.189 | 1.194 | 1.235 | 1.203 | 1.202 |
| The time of losing heart | - | - | - | - | - |
| The leakage time | - | - | - | - | - |
In the over-charging of battery process, adopt the battery of the embodiment of the invention 2 prepared barrier films and FV4365K barrier film all without unusual phenomenon, only find 1 battery leakage that adopts the FS2226-14 barrier film.
(3) self discharge test
Get each 6 of 3 kinds of barrier film experimental cells, 1C charges and discharge its capacity of detection, and the 1C charging is 72 minutes after the 0.2C discharge, and 40 degree baking ovens are shelved and detected its charged conservation rate after 7 days, the results are shown in Table 3.
Table 3 self discharge test
| |
1 | 2 | 3 | 4 | 5 | 6 | mean |
| Initial capacity | 57.68 | 57.73 | 57.65 | 57.20 | 56.62 | 56.55 | 57.24 |
| Shelve the capacity after 7 days | 45.67 | 45.65 | 45.62 | 45.17 | 44.62 | 44.45 | 45.20 |
| Charged conservation rate | 79.18％ | 79.08％ | 79.13％ | 78.97％ | 78.81％ | 78.60％ | 78.96％ |
| FS2226-14 | 1 | 2 | 3 | 4 | 5 | 6 | mean |
| Initial capacity | 55.93 | 55.58 | 56.90 | 57.05 | 57.43 | 56.68 | 56.60 |
| Shelve the capacity after 7 days | 36.25 | 33.62 | 36.40 | 37.60 | 38.12 | 37.32 | 36.55 |
| Charged conservation rate | 64.81％ | 60.49％ | 63.97％ | 65.91％ | 66.38％ | 65.84％ | 64.57％ |
| Barrier film of the |
1 | 2 | 3 | 4 | 5 | 6 | mean |
| Initial capacity | 57.28 | 57.07 | 57.20 | 56.83 | 57.48 | 57.02 | 57.15 |
| Shelve the capacity after 7 days | 43.62 | 43.62 | 43.52 | 43.45 | 44.17 | 43.13 | 43.59 |
| Charged conservation rate | 76.15％ | 76.42％ | 76.08％ | 76.46％ | 76.84％ | 75.64％ | 76.27％ |
From table 3 data as can be known, the charged conservation rate of the barrier film of FV4365K is best, the charged conservation rate of the embodiment of the invention 2 prepared barrier films is better, the charged conservation rate of the barrier film of FS2226-14 is the poorest.The computational methods of charged conservation rate are: battery is shelved capacity after 7 days and the ratio of its initial capacity, is its charged conservation rate.
(4) life test
Table 4 life test
Learn that from table 4 data the cycle life of the battery of the employing embodiment of the invention 2 prepared barrier films is best.
Claims (10)
1. nonwoven fabric of be used for making the Ni-MH battery sulfonated membrane, it is characterized in that, it is a kind of only comprising by mass fraction, the sulfonation nonwoven fabric of 40%～70% sulfonation polypropylene-polyethylene composite short fiber and 30%～60% sulfonation polypropene staple; The fiber number of described sulfonation polypropylene-polyethylene composite short fiber is 1.0dtex～1.5dtex, and the fiber number of described sulfonation polypropene staple is 0.6dtex～1.0dtex; Described sulfonation polypropylene-polyethylene composite short fiber is the composite fibre take polypropylene as inner sandwich layer, take low density polyethylene (LDPE) as exodermis, and the length of described sulfonation polypropylene-polyethylene composite short fiber and sulfonation polypropene staple is 2mm～5mm.
2. the nonwoven fabric for making the Ni-MH battery sulfonated membrane according to claim 1 is characterized in that the length of described sulfonation polypropylene-polyethylene composite short fiber is 2mm～5mm; The length of sulfonation polypropene staple is 3mm～5mm.
3. the nonwoven fabric for making the Ni-MH battery sulfonated membrane according to claim 1, it is characterized in that described sulfonation polypropylene-polyethylene composite short fiber is to be processed with liquid concentrated acid sulfonation separately by polypropylene-polyethylene composite fibre tow to make after the rear sulfonation polypropylene that obtains-polyethylene composite fibre tow cuts off by Len req, described sulfonation polypropene staple is to make after the sulfonation polypropylene fibre tow of acquisition cuts off by Len req after being processed with liquid concentrated acid sulfonation separately by the polypropylene fibre tow.
4. a Ni-MH battery sulfonated membrane is characterized in that adopting the nonwoven fabric for making the Ni-MH battery sulfonated membrane claimed in claim 1 to make.
5. preparation method who be used for to make the nonwoven fabric of Ni-MH battery sulfonated membrane, it is characterized in that, it is to use by mass fraction, 40%～70% sulfonation polypropylene-polyethylene composite short fiber and 30%～60% sulfonation polypropene staple are through making beating, manufacture paper with pulp into net, hot melt typing, hot melt and roll typing and make the sulfonation nonwoven fabric; Described sulfonation polypropylene-polyethylene composite short fiber is the composite fibre take polypropylene as inner sandwich layer, take low density polyethylene (LDPE) as exodermis; The fiber number of described sulfonation polypropylene-polyethylene composite short fiber is 1.0dtex～1.5dtex, and the fiber number of described sulfonation polypropene staple is 0.6dtex～1.0dtex; The length of described sulfonation polypropylene-polyethylene composite short fiber and sulfonation polypropene staple is 2mm～5mm; The preparation of described sulfonation polypropylene-polyethylene composite short fiber in turn includes the following steps:
(A1) preparation of sulfonation polypropylene-polyethylene composite fibre tow
Take polypropylene-polyethylene composite fibre tow as raw material, carry out separately making sulfonation polypropylene-polyethylene composite fibre tow after sulfonation is processed with the liquid concentrated sulfuric acid, the process for sulfonation parameter that adopts is as follows: the sulfonation time is 5min～8min, concentrated sulfuric acid temperature is 114 ℃～120 ℃, and concentrated sulfuric acid concentration is 95%～98%;
(B1) the sulfonation polypropylene that step (A1) is made-polyethylene composite fibre tow cleans up, and comprises first cleaning with dilute sulfuric acid, and then water cleans to the pH value of sulfonation polypropylene-water that the polyethylene composite fibre tow drips and is neutral;
(C1) the sulfonation polypropylene after will cleaning-polyethylene composite fibre tow is pressed Len req and is cut off, and makes sulfonation polypropylene-polyethylene composite short fiber;
The preparation of described sulfonation polypropene staple in turn includes the following steps:
(A2) preparation of sulfonation polypropylene fibre tow
Take the polypropylene fibre tow as raw material, carry out separately making sulfonation polypropylene fibre tow after sulfonation is processed with the liquid concentrated sulfuric acid, the process for sulfonation parameter that adopts is as follows: the sulfonation time is 8min～12min, and concentrated sulfuric acid temperature is 125 ℃～145 ℃, and concentrated sulfuric acid concentration is 95%～98%;
(B2) the sulfonation polypropylene fibre tow that step (A2) is made cleans up, and comprises first with dilute sulfuric acid cleaning, and then the water pH value that cleans the water that drips to sulfonation polypropylene fibre tow is neutral;
(C2) the sulfonation polypropylene fibre tow after will cleaning is pressed Len req and is cut off, and makes the sulfonation polypropene staple.
6. the preparation method of a kind of nonwoven fabric for making the Ni-MH battery sulfonated membrane according to claim 5, it is characterized in that, the length of described sulfonation polypropylene-polyethylene composite short fiber is 2mm～5mm, and the length of described sulfonation polypropene staple is 3mm～5mm.
7. the preparation method of a kind of nonwoven fabric for making the Ni-MH battery sulfonated membrane according to claim 5, it is characterized in that, described step (B1) be sulfonation polypropylene that step (A1) is made-polyethylene composite fibre tow first with concentration be 10%～50%, temperature is that 75 ℃～90 ℃ dilute sulfuric acid cleans, and then water cleans to the pH value of sulfonation polypropylene-water that the polyethylene composite fibre tow drips and is neutral; Described step (B2) be sulfonation polypropylene fibre tow that step (A2) is made first with concentration be 10%～50%, temperature is that 75 ℃～90 ℃ dilute sulfuric acid cleans, and then the pH value that water cleans the water that drips to sulfonation polypropylene fibre tow is neutral.
8. the preparation method of a kind of nonwoven fabric for making the Ni-MH battery sulfonated membrane according to claim 7, it is characterized in that, described step (B1) be sulfonation polypropylene that step (A1) is made-polyethylene composite fibre tow first with concentration be 30%～50%, temperature is that 80 ℃～90 ℃ dilute sulfuric acid cleans, and then water cleans to the pH value of sulfonation polypropylene-water that the polyethylene composite fibre tow drips and is neutral; Described step (B2) be sulfonation polypropylene fibre tow that step (A2) is made first with concentration be 30%～50%, temperature is that 80 ℃～90 ℃ dilute sulfuric acid cleans, and then the pH value that water cleans the water that drips to sulfonation polypropylene fibre tow is neutral.
9. the preparation method of a kind of nonwoven fabric for making the Ni-MH battery sulfonated membrane according to claim 5 is characterized in that in turn including the following steps:
1. the preparation of sulfonation polypropylene-polyethylene composite fibre tow and sulfonation polypropylene fibre tow
Select polypropylene-polyethylene composite fibre tow and polypropylene fibre tow as the raw fiber of the non-woven substrate cloth of making the Ni-MH battery sulfonated membrane, adopt the liquid concentrated sulfuric acid that polypropylene-polyethylene composite fibre tow and polypropylene fibre tow are carried out respectively the sulfonation processing, make sulfonation polypropylene-polyethylene composite fibre tow and sulfonation polypropylene fibre tow; The preparation of wherein said sulfonation polypropylene-polyethylene composite fibre tow may further comprise the steps successively:
(a1) polypropylene-polyethylene composite fibre tow continuous moving enters in the concentrated sulfuric acid bath, contact with the liquid concentrated sulfuric acid and to carry out sulfonation and process, the process for sulfonation parameter that adopts is as follows: the sulfonation time is 5min-8min, and concentrated sulfuric acid temperature is 114 ℃-120 ℃, and concentrated sulfuric acid concentration is 95%-98%;
(b1) the sulfonation polypropylene that obtains after being processed by concentrated acid sulfonation-polyethylene composite fibre tow continues to move in the dilute sulfuric acid rinse bath and cleans with dilute sulfuric acid, to remove the residual concentrated sulfuric acid and the sulfuric acid crystalline solid that adheres between fiber, wherein the dilute sulfuric acid temperature is 80 ℃-90 ℃, and dilute sulfuric acid concentration is 30%-50%;
(c1) the sulfonation polypropylene after dilute sulfuric acid cleans-polyethylene composite fibre tow continues to move into water cleaning in the cleaning sink, cleans to the pH value of sulfonation polypropylene-water that the polyethylene composite fibre tow drips to be neutral;
The preparation of described sulfonation polypropylene fibre tow may further comprise the steps successively:
(a2) polypropylene fibre tow continuous moving enters in the concentrated sulfuric acid bath, contact with the liquid concentrated sulfuric acid and to carry out sulfonation and process, the process for sulfonation parameter that adopts is as follows: the sulfonation time is 8min-12min, and concentrated sulfuric acid temperature is 125 ℃-145 ℃, and concentrated sulfuric acid concentration is 95%-98%;
(b2) the sulfonation polypropylene fibre tow that obtains after being processed by concentrated acid sulfonation continues to move in the dilute sulfuric acid rinse bath and cleans with dilute sulfuric acid: to remove the residual concentrated sulfuric acid and the sulfuric acid crystalline solid that adheres between fiber, wherein the dilute sulfuric acid temperature is 80 ℃-90 ℃, and dilute sulfuric acid concentration is 30%-50%;
(c2) the sulfonation polypropylene fibre tow after dilute sulfuric acid cleans continues to move into that water cleans in the cleaning sink, and the pH value that cleans the water that drips to sulfonation polypropylene fibre tow is neutral;
2. tow cutting: the sulfonation polypropylene that 1. step is made-polyethylene composite fibre tow and sulfonation polypropylene fibre tow cut off by Len req respectively, make sulfonation polypropylene-polyethylene composite short fiber and sulfonation polypropene staple;
3. net, hot melt typing are pulled an oar, manufactured paper with pulp into to batching
The sulfonation polypropylene that 2. step is made-polyethylene composite short fiber and sulfonation polypropene staple mix with water after the proportioning in proportion to be pulled an oar, dilute, disperses, and makes fibre stuff; Fibre stuff dewaters after the wet method machine of manufacturing paper with pulp is manufactured paper with pulp into fiber web, dries hot melting cohesion, cooling forming, rolling, makes semi-products Ni-MH battery sulfonated membrane non-woven substrate cloth;
4. hot melt rolls typing: with 3. prepared semi-products Ni-MH battery sulfonated membrane non-woven substrate cloth of step, individual layer or two stacked add or three layers and above stack are carried out hot melt and rolled compoundly, make for the nonwoven fabric of making the Ni-MH battery sulfonated membrane.
10. the preparation method of a Ni-MH battery sulfonated membrane, it is characterized in that: adopt claim 5,6,7,8 or 9 described preparation methods to make for behind the nonwoven fabric of making the Ni-MH battery sulfonated membrane, carry out again the finish rolling modification and make the Ni-MH battery sulfonated membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101245633A CN101775756B (en) | 2010-03-03 | 2010-03-03 | Non-woven fabric for manufacturing Ni-MH battery sulfonated membrane, Ni-MH battery sulfonated membrane and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101245633A CN101775756B (en) | 2010-03-03 | 2010-03-03 | Non-woven fabric for manufacturing Ni-MH battery sulfonated membrane, Ni-MH battery sulfonated membrane and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101775756A CN101775756A (en) | 2010-07-14 |
| CN101775756B true CN101775756B (en) | 2013-03-27 |
Family
ID=42512328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101245633A Active CN101775756B (en) | 2010-03-03 | 2010-03-03 | Non-woven fabric for manufacturing Ni-MH battery sulfonated membrane, Ni-MH battery sulfonated membrane and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101775756B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569696B (en) * | 2010-12-15 | 2014-05-21 | 莱州联友金浩新型材料有限公司 | Novel nickel-hydrogen battery diaphragm |
| US20140225051A1 (en) * | 2013-02-08 | 2014-08-14 | Ut-Battelle, Llc | Sulfonated polyolefin-based flame retardant material |
| CN109585752B (en) * | 2015-09-30 | 2020-02-18 | 住友化学株式会社 | Film manufacturing method and film manufacturing apparatus |
| JP7014512B2 (en) * | 2015-12-22 | 2022-02-01 | 住友化学株式会社 | Battery separator manufacturing method and battery separator manufacturing equipment |
| CN106835807B (en) * | 2017-01-23 | 2023-07-21 | 吴玉才 | Device for producing natural modeling non-woven fabric non-woven paper by using ultra-long fiber yarns and plant fiber bundles |
| CN109004154B (en) * | 2018-07-23 | 2021-06-18 | 广东蒙泰高新纤维股份有限公司 | Method for manufacturing power lithium ion battery diaphragm by wet papermaking process |
| CN109659471B (en) * | 2018-12-03 | 2021-07-09 | 深圳市量能科技有限公司 | Preparation method of diaphragm and battery diaphragm |
| CN113716547B (en) * | 2021-09-02 | 2023-04-21 | 北京化工大学 | Method for preparing negative electrode material of sodium ion battery by using waste medical mask |
| CN115838995A (en) * | 2022-11-25 | 2023-03-24 | 江苏盛纺纳米材料科技股份有限公司 | Flexible non-woven material and production process thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6120939A (en) * | 1998-01-13 | 2000-09-19 | Daramic, Inc. | Meltblown fiber battery separator |
| CN1747199A (en) * | 2005-07-26 | 2006-03-15 | 天津工业大学 | Production of nickel-hydrogen diaphragm and products thereof |
| CN101153429A (en) * | 2006-09-25 | 2008-04-02 | 天津工业大学 | Method for producing septum substrate cloth of nickel-hydrogen battery with sulphonation method and septum substrate cloth of nickel-hydrogen battery |
| CN101257106A (en) * | 2008-03-13 | 2008-09-03 | 深圳市富易达电子科技有限公司 | Method for modifying polyolefin battery diaphragm paper |
| CN101267028A (en) * | 2008-04-10 | 2008-09-17 | 深圳市富易达电子科技有限公司 | A sulphur-modified polyolefin battery separation film and its making method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2884570B2 (en) * | 1988-04-12 | 1999-04-19 | 日本電池株式会社 | Sealed alkaline secondary battery |
| JP4095190B2 (en) * | 1998-12-17 | 2008-06-04 | 宇部日東化成株式会社 | Sheath-core composite polyolefin fiber and grafted polyolefin nonwoven fabric |
-
2010
- 2010-03-03 CN CN2010101245633A patent/CN101775756B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6120939A (en) * | 1998-01-13 | 2000-09-19 | Daramic, Inc. | Meltblown fiber battery separator |
| CN1747199A (en) * | 2005-07-26 | 2006-03-15 | 天津工业大学 | Production of nickel-hydrogen diaphragm and products thereof |
| CN101153429A (en) * | 2006-09-25 | 2008-04-02 | 天津工业大学 | Method for producing septum substrate cloth of nickel-hydrogen battery with sulphonation method and septum substrate cloth of nickel-hydrogen battery |
| CN101257106A (en) * | 2008-03-13 | 2008-09-03 | 深圳市富易达电子科技有限公司 | Method for modifying polyolefin battery diaphragm paper |
| CN101267028A (en) * | 2008-04-10 | 2008-09-17 | 深圳市富易达电子科技有限公司 | A sulphur-modified polyolefin battery separation film and its making method |
Non-Patent Citations (2)
| Title |
|---|
| JP平1-264167A 1989.10.20 |
| JP特开2000-178832A 2000.06.27 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101775756A (en) | 2010-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101775756B (en) | Non-woven fabric for manufacturing Ni-MH battery sulfonated membrane, Ni-MH battery sulfonated membrane and manufacturing method thereof | |
| CN105702899B (en) | A kind of preparation method of the battery diaphragm containing coating and online coating system | |
| CN105870383B (en) | A kind of battery capacitor barrier film and preparation method thereof | |
| CN102569696B (en) | Novel nickel-hydrogen battery diaphragm | |
| CN103788636B (en) | A kind of polymer blends manufactured for high fineness high intensity non-figured type PA6 superfine fibre | |
| CN108448035B (en) | A kind of lithium ion battery separator and its manufacturing method | |
| CN101872852B (en) | Preparation method of cell diaphragm based on aramid fiber | |
| CN112981722B (en) | Method for preparing lithium ion battery diaphragm by sea island COPET-PP composite negative pressure spinning | |
| CN114441408A (en) | Method for monitoring degree of fibrosis in dry film making process, dry film making method, and preparation method and application of dry electrode plate | |
| CN106450103A (en) | AGM diaphragm for start-stop battery, and preparation method for AGM diaphragm | |
| CN110394273A (en) | A kind of non-woven fabric type lithium ion battery separator single side coating apparatus and coating process | |
| CN101906674A (en) | Efficient washing process for aromatic poly 1,3,4-oxadiazole acid-containing wet silk ribbon | |
| CN101867030A (en) | Battery diaphragm based on aramid fibre | |
| CN201144312Y (en) | Device for manufacturing full drawn yarn/pre-oriented yarn compound yarn by one-step method | |
| CN205587249U (en) | Pole piece preparation system | |
| CN100409466C (en) | Improved accumulator partition | |
| CN104562247A (en) | Dacron anti-radiation wool top production technology | |
| CN108110220A (en) | A kind of high load amount high compacted density lithium ion battery pole piece preparation method | |
| CN116154242A (en) | High-strength polytetrafluoroethylene film and preparation method and application thereof | |
| CN101777635B (en) | Sulfonated battery diaphragm | |
| CN101153429B (en) | Method for producing septum substrate cloth of nickel-hydrogen battery with sulphonation method and septum substrate cloth of nickel-hydrogen battery | |
| CN110181837A (en) | The production method in lithium ion secondary battery membrane control aperture | |
| CN102496464B (en) | Super capacitance battery diaphragm, preparing method thereof and application thereof | |
| CN201689929U (en) | Sulfonated battery diaphragm | |
| CN106684294B (en) | A kind of preparation method of the AGM partition of leachable colloid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: No. 87, former Yang Industrial Zone, Qishuyan District, Changzhou, Jiangsu Province Patentee after: CHANGZHOU KANGJIE SPECIAL NON-WOVEN FABRICS CO., LTD. Address before: No. 87, former Yang Industrial Zone, Qishuyan District, Changzhou, Jiangsu Province Patentee before: Kangjie Battery Materials Co., Ltd., Changzhou City |