CN101257106A - Method for modifying polyolefin battery diaphragm paper - Google Patents
Method for modifying polyolefin battery diaphragm paper Download PDFInfo
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- CN101257106A CN101257106A CNA2008100345745A CN200810034574A CN101257106A CN 101257106 A CN101257106 A CN 101257106A CN A2008100345745 A CNA2008100345745 A CN A2008100345745A CN 200810034574 A CN200810034574 A CN 200810034574A CN 101257106 A CN101257106 A CN 101257106A
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Abstract
The invention discloses a modification technology for polyolefin battery separator paper which has steps as follows: paper with tightness 0.250-0.350 g/cm<3> is processed by using paper processing method according with suitable proportion of PP fibre and ES fibre; putting polyolefin paper in plasma generator, inletting working gas after vacuumizing, opening RF electrical source, processing 3-10min, taking out sample; putting processed paper sample in acrylic acid aqueous solution with temperature 65-75 DEG C for reacting, taking out paper sample, washing residual acrylic, and boiling 1-3h, finally, drying in oven with temperature 65-80 DEG C. Paper hydrophilic property can be increased greatly after being processed, and alkali absorbing rate and amount are larger and exceed 20%, surface resistance is lower than present lithium ion battery, thereby, various performance indicators are better than present battery.
Description
Technical field
The present invention relates to a kind of modification technology field to polyolefin battery diaphragm paper.
Background technology
Along with developing rapidly of microelectric technique, greatly promoted the quickening of mobile communication and computer industry update paces.Electric elements are required that volume is littler, and function is more complete, and stand-by time is longer.For this reason, the battery in the charge storage element just becomes and wherein requires one of improved critical elements.And battery diaphragm is called battery " the 3rd utmost point ", be one of important component part of cadmium 2 nickel, hydrogen 2 nickel-based batteries, play the isolation anode and cathode and do not make battery be short-circuited Electolyte-absorptive, conductive ion can be passed through smoothly, and allow effects such as gas permeation barrier film.The quality of its quality directly has influence on the charge-discharge performance, high temperature performance of battery, charged storage and useful life or the like, therefore requires battery diaphragm material must have excellent acid alkalescence and low resistive.Usually battery diaphragm more options synthetic fibers are as Fypro, poly-ethanol fiber, polypropylene fibre, polyester fiber, polyolefine fiber etc., wherein polyolefine fiber is with its good resistance to wear, elasticity, excellent acid and alkali-resistance, oxidative resistance, heat-resisting quantity and in light weight be preferred material.But the hydrophily extreme difference of polyolefine fiber must carry out modification to it and handle, and just can satisfy the requirement of battery diaphragm.
The U.S., Japan successfully use it for batteries such as mobile phone, and the domestic conceptual phase that still is in this regard, cadmium 2 nickel, hydrogen 2 nickel-based battery diaphragm materials are dependence on import basically.Do not have hydrophilic radical in the molecular structure of polyolefine fiber, and degree of crystallinity is very high, the fibre section is rounded, has strong hydrophobicity, and its diaphragm forming adopts hot rolling or producing technology of non-woven fabrics such as spunbond more.
Many outstanding advantages such as lithium-ions battery is in light weight, and energy storage is big, and power is big, and is pollution-free, and the life-span is long, and the self discharge coefficient is little, and temperature accommodation is wide in range.The critical material of lithium-ion-power cell has following four aspects: positive electrode, negative material, electrolyte and barrier film.Wherein the lithium salts in barrier film and electrolyte still relies on the external import at present, and other critical material all domesticizes.In Unit Weight and unit volume energy storage, charge-discharge performance, the Applicable temperature scope discharges and recharges performances such as number of times, has all reached international indicator.The problem of current existence is the consistency and the safety problem of battery.For electric bicycle, do the lithium-ions battery of positive electrode with LiMn2O4, can enough guarantee the safety that it travels.If the price of noticing the manganese on the international market again is than cheap a lot of of the price of cobalt.So in the promotion and application of lithium-ions battery, the improvement of its security performance may make manufacturing cost decrease on the contrary! Along with improving constantly and progress of science and technology of living standards of the people, cadmium nickel battery, nickel-hydrogen battery are more and more accepted by people.Cadmium nickel battery, nickel-hydrogen battery have discharge and recharge often (can reach more than 500 times) but, premium properties such as long fast charging and discharging of life-span, high-multiplying power discharge, overcharging resisting electricity.
The maximum difficult point of current existence is, the used barrier film of lithium-ions battery has been failed substantial breakthrough.China produces each producer of lithium ion battery, all depends on external import, and its price is even accounted for more than 20% of production cost! In fact, what precious materials the used barrier film of lithium ion battery is not, just China so far the technology aspect large-scale production do not reach a standard yet! If these technological difficulties are solved, the production cost of China's lithium-ions battery can also descend significantly.
But premium properties such as alkaline secondary cell discharges and recharges often owing to having, long fast charging and discharging, high-multiplying power discharge and overcharging resisting of life-span are more and more paid attention to by people.But there are very big gap all the time in homemade alkaline secondary cell of China and import battery such as Panasonic, Toshiba etc., and wherein the quality problems of battery diaphragm are one of major reasons.Improving membrane properties is to improve the most direct means of battery cycle life.Because polypropylene non-woven fabric has the chemical stability of height such as alkaline-resisting, resistance to oxidation, series of advantages such as mechanical strength and toughness preferably, it is comparatively desirable battery diaphragm base material, but its suction alkali speed and alkalis suction quantity are lower, and face resistance is big, become the basic reason of its extensive use of restriction.
Summary of the invention
The purpose of this utility model is to provide a kind of modification technology to polyolefin battery diaphragm paper, improves the serviceability of existing polyolefin battery diaphragm paper.
The principle of the inventive method: plasma is a kind of gas that has enough charged quantity and equal positive and negative charge number is arranged, and when the charged particle densities of gas ionization generation reached certain numerical value, the state of material can change and produce plasma.Plasma contains compositions such as electronics, ground atom and molecule, excited state particle and photon usually, it is a kind of gaseous conductor, keep electric neutrality on the whole, and exist electrical property difference, thereby in whole system, have the interaction between electric field and charged particle in the part.When having dynamic excitation, the charged particle in the plasma is able to continuous acceleration, when promoting himself energy, by mutual collision, with Conversion of energy or transfer.In the time of on these energy or upper state particle affact as the fiber material of matrix, can produce complex physico-chemical such as heating, etching, radical reaction, the alkyl of PP is transformed into carbonyl, carboxyl, hydroxyl isopolarity group, then with acrylic acid-grafted, the result makes the unformed area of fiber surface increase, it is big that specific area becomes, and hydrophily increases substantially.
The present invention is composite by PP polypropylene fibre and ES polyethylene/polypropylene bicomponent fibre, employing can control evenness, quantitatively, be suitable for the industrial wet papermaking process synthetic fiber paper of manufacturing paper with pulp out, using plasma equipment again, by argon gas pattern is handled, carry out acrylic acid-grafted then, improve the hydrophilicity of paper greatly, made it to be suitable for use as battery diaphragm.
The concrete technical scheme that the present invention takes is as follows:
Method to the polyolefin battery diaphragm paper modification the steps include:
D, with PP fiber and ES fiber by suitable proportioning, adopting the paper process tightness of manufacturing paper with pulp out is the paper of 0.250～0.350g/cm3.
E, polyolefins paper is placed plasma generator, vacuumize the back and feed working gas, open radio-frequency power supply, handle 3～10min, take out sample.
F, the pattern after handling is put into temperature is that 65～75 ℃ of acrylic acid aqueous solutions react, and takes out pattern, and the acrylic acid of flush away remnants boils 1～3h with boiling water again, dries in 65～80 ℃ baking oven at last.
Above-mentioned step a, the weight proportion of PP fiber and ES fiber is 1: 10～0.5～2.
Above-mentioned step b, vacuum degree preferably is transferred to required operating air pressure 10～30Pa; The working gas that feeds is an argon.
Above-mentioned step c, the concentration of acrylic acid aqueous solution is preferably 15～40%.
Beneficial effect of the present invention: utilize method of the present invention that polyolefin battery diaphragm paper is carried out the plasma modification, argon plasma processing graft acrylic acid has greatly improved to the water absorption of polyolefins paper.Change isoionic discharge power, to polyolefins paper, very big influence is arranged acrylic acid-grafted.After the processing, improved the hydrophilicity of paper greatly, its suction alkali speed and alkalis suction quantity are bigger, surpass 20%, and face resistance is also little than existing lithium ion battery, and therefore, every performance index obviously are better than existing battery.
Description of drawings
Fig. 1 is the surface of untreated polyolefins paper
Fig. 2 is the surface picture of polyolefins paper after the plasma treatment
Embodiment
One, raw material and instrument
1, PP fiber, polyethylene/polypropylene ES fiber;
2, acrylic acid, chemical pure;
3, plasma generator, power emission source: SY type 300W radio frequency power source, Chinese Academy of Sciences's microelectronics center;
4, tensile strength tester; Contact angle instrument J C2000; The multimedia microscope; The PE2783 infrared spectrophotometer.
Two, experimental technique
1, sample preparation
PP fiber and ES fiber by certain proportioning, are discongested that to disperse the back to adopt the paper process tightness of manufacturing paper with pulp out be the paper of 0.250g/cm3.
2, plasma treatment
Polyolefins paper is placed plasma generator, open the vacuum suction valve, after the vacuum degree of waiting to reach certain, feed working gas, vacuum degree is transferred to required operating air pressure 40Pa, open radio-frequency power supply, handle certain hour, powered-down takes out sample.
4, acrylic acid-grafted
It is 60 ℃ that pattern after handling is put into temperature, and concentration is to react 1h in 20% the acrylic acid aqueous solution, takes out pattern, and the acrylic acid of clear water flush away remnants boils 3h with boiling water again, last in 60 ℃ baking oven dry for standby.
5, method of testing
1) percent grafting is measured with Weighing method.
Percent grafting G (%)=(Mg-M0)/M0 M0, Mg are respectively the quality g before and after the grafting.
2) performance test
Alkali absorbing rate, suction alkali height are by Japanese battery diaphragm standard testing.
A, tensile index detect
On pendulum paper tension stress testing machine, carry out the tension stress test of sample.
Tensile index Nm/g X=Gp/W Gp, W are respectively absolute tensile strength N/m, quantitative g/m
B, measurement of contact angle
Adopt static method to measure the contact angle on polyolefins paper surface.
C, the microscopical test of multimedia
The polyolefins paper test piece is placed under the projecting apparatus, it is amplified 400 times, observe the surface of paper.
D, infrared spectrum measurement
Polyolefine fiber paper is cut into powder,, sample is detected with the PE2783 infrared spectrophotometer with pressing potassium bromide troche.
Three, result and discussion
Argon gas is a non-reactive gas, this gas atom does not directly enter into the macromolecular chain on high polymer material surface, but because the energy delivery of high-energy particle bombardment material surface in these non-reactive gas plasmas, make the material surface activation and produce a large amount of free radicals.Discharge power has very big effect to the activation of polyolefins paper fiber surface, and therefore, this paper controls the pressure 40Pa of argon gas, processing time 3min, acrylic acid solution concentration 20%, 60 ℃ of temperature, the graft reaction time is 1h, changes plasma discharge power, and the influence of following performance to paper is discussed.
Discharge power is to the influence of polyolefins paper percent grafting and tensile index
The best power of handling this tightness polyolefins paper is 20～35W.Can analyze from influence: the activation that act as group on plasma and polyolefins paper surface, crosslinked, surface etch and vie each other percent grafting and tensile index.Under lower power, the self-energy of charged particle is less in the plasma, and activation is greater than crosslinked corrasion.At it and when acrylic acid-grafted, percent grafting is higher.Acrylic acid content that grafting is got on also increases with it, produce hydrogen bond between the carbonyl, the tensile strength of paper a little a bit increases, increase along with plasma discharge power, the charged particle energy increases, it is leading that crosslinked corrasion has occupied, and causes active group quantity to descend, the variation tendency that the result descends after causing grafting to take the lead in liter.Crosslinked etching reduces paper fiber surface crystal region and the unformed area increase, so the tensile strength of paper has reduction slightly.Generally speaking, plasma discharge power is not very big to the tensile strength influence of polyolefins paper.
Discharge power is to the influence of alkali absorbing rate and suction alkali height
Be the influence of discharge power to polyolefins paper alkali absorbing rate and suction alkali height.The suction alkali ability of polyolefins paper is most important as battery diaphragm to it, general alkali absorbing rate and suction alkali height can reflect the suction alkali ability of battery diaphragm to a certain extent, for battery diaphragm, it is big more to inhale the alkali height, ion in the electrolyte is easy more to be passed through, and make the chemical reaction of negative electrode and anode abundant more, battery capacity is big more.
Plasma discharge power is inhaled the influence of alkali height and alkali absorbing rate to polyolefins paper
Inhaling the alkali height simultaneously also is a reflection of inhaling alkali speed, is another important indicator of hydrophilicity quality and inhale alkali speed.The alkali absorbing rate of polyolefins paper and suction alkali height are to fall after rising with the increase of discharge power all.This may be because of the increase along with discharge power, and the free radical that the paper surface is activated is more and more, and under the certain reaction temperature, its causes the percent grafting increase of acrylic acid to polyolefins paper, makes the paper surface produce some oxy radicals; Can form hydrogen bond between these groups and the hydrone, paper is diminished to the contact angle of water, therefore, alkali absorbing rate and suction alkali height raise gradually.But along with the further increase of discharge power, alkali absorbing rate and inhale the alkali height and reduce on the contrary, this may be because plasma to the introducing greater than active group of the crosslinked etching power on paper surface, and makes due to percent grafting descends.
The sign of the acrylic acid polyolefins paper of plasma initiation grafting
Electron microscope observation paper surface
Fig. 1 and Fig. 2 are the electron microscope observation figure of acrylic acid-grafted front and back polyolefins paper, and as can be seen from Figure, the fiber on untreated polyolefins paper surface is smooth; After argon plasma was handled grafting, the rough surface of sample had variable grain size thrust to occur, and the fiber surface acrylic acid hydrophilic radical in the also grafting that has been etched be described.
Contact angle and hydrophilic mensuration
With the increase of plasma discharge power, the contact angle of polyolefins paper also has a minimum value, promptly maximum hydrophilicity.So with argon plasma synthetic fiber paper is carried out carrying out grafting after the modification, can greatly improve the hydrophilicity of paper.
The plasma radiant power is to the influence of polyolefins paper contact angle
Radiant power/W 0 20 30 45 60 75
Contact angle/° 136 20 8 15 50 52
The IR Characterization of graft
After the pure polyolefine fiber grafting, can find that tangible 1720cm-1 carbonyl characteristic absorption peak is arranged on the spectral line of graft, show that acrylic monomers has been grafted on the polyolefine fiber by the INFRARED SPECTRUM of polyolefine fiber.
Conclusion
1, argon plasma processing graft acrylic acid has greatly improved to the water absorption of polyolefins paper.
2, change isoionic discharge power, to polyolefins paper, very big influence is arranged acrylic acid-grafted.The optimised process that draws the plasma treatment polyolefins paper is: power 30W, discharge time 3min, control argon gas pressure 40Pa.When acrylic acid-grafted, the concentration of acrylic acid aqueous solution is 20%, 60 ℃ of reaction temperatures, and the reaction time is 1h.Rate surpasses 20%, obviously is better than existing battery.
Claims (5)
1, to the method for polyolefin battery diaphragm paper modification, the steps include:
A, with PP fiber and ES fiber by suitable proportioning, adopting the paper process tightness of manufacturing paper with pulp out is the paper of 0.250～0.350g/cm3;
B, polyolefins paper is placed plasma generator, vacuumize the back and feed working gas, open radio-frequency power supply, handle 3～10min, take out sample;
C, the pattern after handling is put into temperature is that 65～75 ℃ of acrylic acid aqueous solutions react, and takes out pattern, and the acrylic acid of flush away remnants boils 1～3h with boiling water again, dries in 65～80 ℃ baking oven at last.
2, the method to the polyolefin battery diaphragm paper modification as claimed in claim 1 is characterized in that: among the step a, the weight proportion of PP fiber and ES fiber is 1: 10～0.5～2.
3, the method to the polyolefin battery diaphragm paper modification as claimed in claim 1 is characterized in that: among the step b, vacuum degree is 10～30Pa.
4, the method to the polyolefin battery diaphragm paper modification as claimed in claim 1 is characterized in that: among the step b, the working gas of feeding is an argon.
5, the method to the polyolefin battery diaphragm paper modification as claimed in claim 1 is characterized in that: among the step c, the concentration of acrylic acid aqueous solution is 15～40%.
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| CNA2008100345745A CN101257106A (en) | 2008-03-13 | 2008-03-13 | Method for modifying polyolefin battery diaphragm paper |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775756A (en) * | 2010-03-03 | 2010-07-14 | 常州市康捷电池材料有限公司 | Non-woven fabric for manufacturing Ni-MH battery sulfonated membrane, Ni-MH battery sulfonated membrane and manufacturing method thereof |
| CN102054953A (en) * | 2010-12-10 | 2011-05-11 | 苏州大学 | Processing method of septum for secondary lithium battery as well as secondary lithium battery |
| CN106592322A (en) * | 2016-10-10 | 2017-04-26 | 天津科技大学 | Method for preparing alkaline battery diaphragm paper |
-
2008
- 2008-03-13 CN CNA2008100345745A patent/CN101257106A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775756A (en) * | 2010-03-03 | 2010-07-14 | 常州市康捷电池材料有限公司 | Non-woven fabric for manufacturing Ni-MH battery sulfonated membrane, Ni-MH battery sulfonated membrane and manufacturing method thereof |
| CN101775756B (en) * | 2010-03-03 | 2013-03-27 | 常州市康捷电池材料有限公司 | Non-woven fabric for manufacturing Ni-MH battery sulfonated membrane, Ni-MH battery sulfonated membrane and manufacturing method thereof |
| CN102054953A (en) * | 2010-12-10 | 2011-05-11 | 苏州大学 | Processing method of septum for secondary lithium battery as well as secondary lithium battery |
| CN106592322A (en) * | 2016-10-10 | 2017-04-26 | 天津科技大学 | Method for preparing alkaline battery diaphragm paper |
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Open date: 20080903 |