CN107946522A - A kind of graphene oxide is modified nickel-hydrogen battery separator and preparation method thereof - Google Patents
A kind of graphene oxide is modified nickel-hydrogen battery separator and preparation method thereof Download PDFInfo
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- CN107946522A CN107946522A CN201711344823.6A CN201711344823A CN107946522A CN 107946522 A CN107946522 A CN 107946522A CN 201711344823 A CN201711344823 A CN 201711344823A CN 107946522 A CN107946522 A CN 107946522A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
A kind of graphene oxide is modified nickel-hydrogen battery separator and preparation method thereof, belongs to Ni-MH battery field.The membrane is made using two-component skin-core structure fiber as fibrous raw material, and the cortex of the two-component skin-core structure fiber is composite fibre made from polyethylene fibre and graphene oxide fiber, wherein, the weight ratio of polyethylene fiber peacekeeping graphene oxide fiber is 2 ~ 5：1；The sandwich layer of the two-component skin-core structure fiber is polypropylene fibre, and the mass ratio of cortex and sandwich layer is 1 ~ 3：1, meanwhile, make membrane that there is hydrophily by sulfonation processing and protect fluidity.Nickel-hydrogen battery separator prepared by the present invention has stronger mechanical performance, chemical stability and dimensional stability and preferable hydrophily and protects fluidity, improves the performance of Ni-MH battery.
Description
Technical field
A kind of graphene oxide is modified nickel-hydrogen battery separator and preparation method thereof, belongs to Ni-MH battery field.
Background technology
With attention of the people to environmental issue, people are to free of contamination " green battery " --- and Ni-MH battery is increasingly heavier
Depending on.The popularization and application of especially present electric automobile so that study more efficient Ni-MH battery tool and be of great significance.
Ni-MH battery is mainly made of critical materials such as positive and negative electrode and battery separator papers.Battery diaphragm is to be used to separate
Directly contacting for battery positive and negative electrode, causes the inorganic or organic film of battery short circuit.Battery diaphragm as in Ni-MH battery can not or
Scarce part, the quality of diaphragm material performance is to the capacity of Ni-MH battery, self discharge, discharge voltage, service life cycle and peace
Full property and cost etc. can all produce large effect.Therefore, studying high performance nickel-hydrogen battery separator has extremely important meaning.
Battery diaphragm is as the isolation board between the positive and negative anodes of battery, it is necessary to possess good non-conductive property, can with prevention
The battery short circuit phenomenon that can occur.Because it is in the electrolytic solution in soaking state, then must possess have to electrolyte it is good
Antioxygenic property, its size hole also allow for preventing particle flow etc. between electrode.Therefore it is most to prepare nickel-hydrogen battery separator
Select within the scope of wider temperature (- 55 DEG C ~ 85 DEG C), stability can be kept, particularly chemical stability, to electronics in height
Resistance, is in low-resistance to ion, easy to the as far as possible thin battery diaphragm of gas diffusion.
In recent years, the performance of the domestic nickel-hydrogen battery separator in China had certain rising, but the matter of such domestic product
Amount is not still very stable.According to the introduction of Ni-MH battery factory, the Ni-MH battery for producing top grade at home stills need to use the nickel of import
Hydrogen battery membrane, the level of domestic battery diaphragm product have much room for improvement.Therefore exploitation high-performance nickel-hydrogen battery separator, improvement China
Membrane production technology, the application to China's battery power have extremely important meaning.
The content of the invention
The technical problem to be solved in the present invention is：Overcome the deficiencies of the prior art and provide a kind of graphene oxide Modified Nickel
The preparation method of hydrogen battery membrane, the method prepare nickel-hydrogen battery separator it is conductive it is poor, protect fluidity height, wellability it is good,
The features such as anti-electrolytic corrosion height and good stability of the dimension.
The technical solution adopted by the present invention to solve the technical problems is：Using two-component skin-core structure fiber as fibrous raw material
It is made, two-component skin-core structure fiber includes cortex and sandwich layer, and the cortex is polyethylene fibre and graphene oxide fiber system
The composite fibre obtained, wherein, the weight ratio of polyethylene fiber peacekeeping graphene oxide fiber is 2 ~ 5：1；The sandwich layer is polypropylene
The mass ratio of fiber, cortex and sandwich layer is 1 ~ 3：1.
Preferably, the weight ratio of the polyethylene fiber peacekeeping graphene oxide fiber is 3：1.
Preferably, the mass ratio of the cortex and sandwich layer is 2：1.
The core layer length is 10 ~ 20mm, and fiber number is 0.6 ~ 1.2tex, and cortex length is 10 ~ 20mm, fiber number for 0.8 ~
1.65tex。
Preferably, the core layer length is 13 ~ 20mm, and fiber number is 0.8 ~ 1.2tex, and cortex length is 13 ~ 18mm, fiber number
For 0.9 ~ 1.5tex.
Polyethylene fibre and graphene oxide random packing of fibers in the cortex.
Graphene oxide is modified the preparation method of nickel-hydrogen battery separator, it is characterised in that：Comprise the following steps：
1）Wet method is hot-forming：Fibrous raw material is diluted, is discongested, it is scattered prepare slurry, then by wet method manufacture paper with pulp online into
Type, is finally made non-weaving cloth base fabric by dehydration, heated-air drying, hot rolling and pressure-sizing modification, and hot-rolled temperature is 120 ~ 140 DEG C,
The hot rolling time is 15 ~ 35min, and pressure is 1.0 ~ 3.0kg/cm2；
2）Sulfonation is handled：Base fabric is put into sulfur trioxide sulfonation reactor, walk cloth 12 ~ 18m/min of speed, reactor temperature
For 40 ~ 55 DEG C, the concentration of sulfur trioxide is 90 ~ 95%, obtains the strong battery diaphragm base fabric of hydrophily after sulfonation；
3）Sulfonation post-processes：Battery diaphragm base fabric after above-mentioned steps are handled is washed 1 ~ 2 time in 60 ~ 70% sulfuric acid, washing
Time is 4 ~ 6min, then using 20 ~ 30% sulfuric acid scrubbing 1 ~ 2 time, wash time is 5 ~ 8min, is finally floated with deionized water
Wash 2 ~ 3 times, wash time is 6 ~ 10min, and drying, plate, and obtains the nickel-hydrogen battery separator of graphene oxide modification.
Preferably, the step 1）Middle hot-rolled temperature is 125 ~ 135 DEG C, and the hot rolling time be 20-30min, pressure is 1.5 ~
2.5kg/cm2。
Preferably, step 2）Described in sulfonation processing walk cloth speed be 16m/min, reactor temperature is 45 DEG C, three
The concentration of sulfur oxide is 93%.
Preferably, step 3）60 ~ 70% sulfuric acid scrubbing time is 5min in described sulfonation post processing, 20 ~ 30% sulphur
The acid elution time is 7min, and the time of deionized water rinsing is 8.5min.
Preferably, step 3）Described in the temperature dried be 90 ~ 100 DEG C, time of drying is 40 ~ 70min, the temperature of pressing
Spend for 80 ~ 90 DEG C.
Graphene oxide（GO）It is a kind of derivative of graphene, the two-dimensional network structure with single layer of carbon atom, with stone
Unlike black alkene, surface of graphene oxide is dispersed with the polarity oxygen-containing functional group including carboxyl, epoxy group and hydroxyl, this
A little functional groups cause graphene oxide to have excellent dispersed, extremely low electrical conductivity and the compatibility with polymer, these property
Matter is fully compatible for application of the graphene oxide on nickel-hydrogen battery separator.
Compared with prior art, beneficial effect possessed by the present invention is：Graphene oxide Modified Nickel prepared by the present invention
Hydrogen battery membrane, utilizes excellent dispersed, the extremely low electrical conductivity of graphene oxide fiber and special with the compatibility of polymer etc.
Property so that the modification Ni-MH battery membrane conductivity of preparation is poor, protects that fluidity is high, wellability is good, anti-electrolytic corrosion is high and ruler
Very little stability is good, and stretch-proof fracture strength reaches 168 ~ 180N/15mm, and alkali absorbing rate reaches 548 ~ 620%, inhale alkali speed 15 ~
21cm/30min, vertical and horizontal percent thermal shrinkage substantially reduce, and reach 1.9% and 1.2%, also, graphene oxide helps to change
The corrosion resistance of kind diaphragm material, and effectively reduce the electric conductivity of membrane.
Embodiment
With reference to embodiment, the present invention will be further described, and embodiment 1 is most preferred embodiment.
Embodiment 1
The weight ratio of polyethylene fiber peacekeeping graphene oxide fiber is 3 in the present embodiment nickel-hydrogen battery separator fibrous material：1, skin
The mass ratio of layer and sandwich layer is 2：1, core layer length 15mm, fiber number 1.0tex, cortex length are 15mm, and fiber number is
1.2tex。
Preparation method：1）Wet method is hot-forming：Fibrous raw material is diluted, is discongested, disperses to prepare slurry, then through overly moist
Method is manufactured paper with pulp upper net forming, is finally modified by dehydration, heated-air drying, hot rolling and pressure-sizing and non-weaving cloth base fabric, hot-rolled temperature is made
For 130 DEG C, the hot rolling time is 25min, pressure 2.0kg/cm2。
2）Sulfonation is handled：Base fabric is put into sulfur trioxide sulfonation reactor, walk cloth speed 16m/min, it is warm in reactor
Spend for 45 DEG C, the concentration of sulfur trioxide is 93%, obtains the strong battery diaphragm base fabric of hydrophily after sulfonation.
3）Sulfonation post-processes：Battery diaphragm base fabric after above-mentioned steps are handled is washed 2 times in 60 ~ 70% sulfuric acid, is washed
It is 5min to wash the time, then using 20 ~ 30% sulfuric acid scrubbing 2 times, wash time 7min, finally with deionized water rinse 3
Secondary, wash time 8.5min, 60min is dried at 95 DEG C, is plated at 85 DEG C, obtain the Ni-MH battery of graphene oxide modification every
Film.
Embodiment 2
The weight ratio of polyethylene fiber peacekeeping graphene oxide fiber is 2 in the present embodiment nickel-hydrogen battery separator fibrous material：1, skin
The mass ratio of layer and sandwich layer is 1：1, core layer length 15mm, fiber number 1.0tex, cortex length are 15mm, and fiber number is
1.2tex。
Preparation method is the same as embodiment 1.
Embodiment 3
The weight ratio of polyethylene fiber peacekeeping graphene oxide fiber is 5 in the present embodiment nickel-hydrogen battery separator fibrous material：1, skin
The mass ratio of layer and sandwich layer is 3：1, core layer length 15mm, fiber number 1.0tex, cortex length are 15mm, and fiber number is
1.2tex。
Preparation method is the same as embodiment 1.
Embodiment 4
The weight ratio of polyethylene fiber peacekeeping graphene oxide fiber is 3 in the present embodiment nickel-hydrogen battery separator fibrous material：1, skin
The mass ratio of layer and sandwich layer is 2：1, core layer length 10mm, fiber number 0.6tex, cortex length are 15mm, and fiber number is
0.8tex。
Preparation method is the same as embodiment 1.
Embodiment 5
The weight ratio of polyethylene fiber peacekeeping graphene oxide fiber is 3 in the present embodiment nickel-hydrogen battery separator fibrous material：1, skin
The mass ratio of layer and sandwich layer is 2：1, core layer length 20mm, fiber number 1.2tex, cortex length are 10mm, and fiber number is
1.65tex。
Preparation method is the same as embodiment 1.
Embodiment 6
The weight ratio of polyethylene fiber peacekeeping graphene oxide fiber is 3 in the present embodiment nickel-hydrogen battery separator fibrous material：1, skin
The mass ratio of layer and sandwich layer is 2：1, core layer length 15mm, fiber number 1.0tex, cortex length are 15mm, and fiber number is
1.2tex。
Preparation method：1）Wet method is hot-forming：Fibrous raw material is diluted, is discongested, disperses to prepare slurry, then through overly moist
Method is manufactured paper with pulp upper net forming, is finally modified by dehydration, heated-air drying, hot rolling and pressure-sizing and non-weaving cloth base fabric, hot-rolled temperature is made
For 120 DEG C, the hot rolling time is 25min, pressure 2.5kg/cm2。
2）Sulfonation is handled：Base fabric is put into sulfur trioxide sulfonation reactor, walk cloth speed 12m/min, it is warm in reactor
Spend for 45 DEG C, the concentration of sulfur trioxide is 93%, obtains the strong battery diaphragm base fabric of hydrophily after sulfonation.
3）Sulfonation post-processes：Battery diaphragm base fabric after above-mentioned steps are handled is washed 1 time in 60 ~ 70% sulfuric acid, is washed
It is 4min to wash the time, then using 20 ~ 30% sulfuric acid scrubbing 2 times, wash time 8min, finally with deionized water rinse 3
Secondary, wash time 10min, 40min is dried at 90 DEG C, is plated at 90 DEG C, obtain the Ni-MH battery of graphene oxide modification every
Film.
Embodiment 7
The weight ratio of polyethylene fiber peacekeeping graphene oxide fiber is 3 in the present embodiment nickel-hydrogen battery separator fibrous material：1, skin
The mass ratio of layer and sandwich layer is 2：1, core layer length 15mm, fiber number 1.0tex, cortex length are 15mm, and fiber number is
1.2tex。
Preparation method：1）Wet method is hot-forming：Fibrous raw material is diluted, is discongested, disperses to prepare slurry, then through overly moist
Method is manufactured paper with pulp upper net forming, is finally modified by dehydration, heated-air drying, hot rolling and pressure-sizing and non-weaving cloth base fabric, hot-rolled temperature is made
For 140 DEG C, the hot rolling time is 15min, pressure 3.0kg/cm2。
2）Sulfonation is handled：Base fabric is put into sulfur trioxide sulfonation reactor, walk cloth speed 18m/min, it is warm in reactor
Spend for 40 DEG C, the concentration of sulfur trioxide is 90%, obtains the strong battery diaphragm base fabric of hydrophily after sulfonation.
3）Sulfonation post-processes：Battery diaphragm base fabric after above-mentioned steps are handled is washed 2 times in 60 ~ 70% sulfuric acid, is washed
It is 6min to wash the time, then using 20 ~ 30% sulfuric acid scrubbing 1 time, wash time 5min, finally with deionized water rinse 2
Secondary, wash time 6min, 70min is dried at 100 DEG C, is plated at 80 DEG C, obtain the Ni-MH battery of graphene oxide modification every
Film.
Embodiment 8
The weight ratio of polyethylene fiber peacekeeping graphene oxide fiber is 3 in the present embodiment nickel-hydrogen battery separator fibrous material：1, skin
The mass ratio of layer and sandwich layer is 2：1, core layer length 15mm, fiber number 1.0tex, cortex length are 15mm, and fiber number is
1.2tex。
Preparation method：1）Wet method is hot-forming：Fibrous raw material is diluted, is discongested, disperses to prepare slurry, then through overly moist
Method is manufactured paper with pulp upper net forming, is finally modified by dehydration, heated-air drying, hot rolling and pressure-sizing and non-weaving cloth base fabric, hot-rolled temperature is made
For 125 DEG C, the hot rolling time is 35min, pressure 1.0kg/cm2。
2）Sulfonation is handled：Base fabric is put into sulfur trioxide sulfonation reactor, walk cloth speed 15m/min, it is warm in reactor
Spend for 50 DEG C, the concentration of sulfur trioxide is 95%, obtains the strong battery diaphragm base fabric of hydrophily after sulfonation.
3）Sulfonation post-processes：Battery diaphragm base fabric after above-mentioned steps are handled is washed 2 times in 60 ~ 70% sulfuric acid, is washed
It is 5min to wash the time, then using 20 ~ 30% sulfuric acid scrubbing 1 time, wash time 6min, finally with deionized water rinse 2
Secondary, wash time 8min, 500min is dried at 100 DEG C, is plated at 85 DEG C, obtain the Ni-MH battery of graphene oxide modification every
Film.
Comparative example 1
This comparative example selects polyethylene and polypropylene composite materials fiber, and as fibrous raw material, preparation method is the same as embodiment 1.
Comparative example 2
It is fibrous raw material that this comparative example, which selects two-component skin-core structure fiber, polyethylene fiber in the two-component skin-core structure fiber
The weight ratio of peacekeeping graphene oxide fiber is 6：1, the mass ratio of cortex and sandwich layer is 4：1, core layer length 15mm, fiber number are
1.0tex, cortex length are 15mm, fiber number 1.2tex.
Preparation method is the same as embodiment 1.
Comparative example 3
It is fibrous raw material that this comparative example, which selects two-component skin-core structure fiber, polyethylene fiber in the two-component skin-core structure fiber
The weight ratio of peacekeeping graphene oxide fiber is 1：1, the mass ratio of cortex and sandwich layer is 1：2, core layer length 25mm, fiber number are
1.5tex, cortex length are 10mm, fiber number 0.6tex.
Preparation method is the same as embodiment 1.
Comparative example 4
The weight ratio of polyethylene fiber peacekeeping graphene oxide fiber is 3 in the present embodiment nickel-hydrogen battery separator fibrous material：1, skin
The mass ratio of layer and sandwich layer is 2：1, core layer length 15mm, fiber number 1.0tex, cortex length are 15mm, and fiber number is
1.2tex。
Preparation method：1）Wet method is hot-forming：Fibrous raw material is diluted, is discongested, disperses to prepare slurry, then through overly moist
Method is manufactured paper with pulp upper net forming, is finally modified by dehydration, heated-air drying, hot rolling and pressure-sizing and non-weaving cloth base fabric, hot-rolled temperature is made
For 150 DEG C, the hot rolling time is 40min, pressure 3.5kg/cm2。
2）Sulfonation is handled：Base fabric is put into sulfur trioxide sulfonation reactor, walk cloth speed 10m/min, it is warm in reactor
Spend for 60 DEG C, the concentration of sulfur trioxide is 95%, obtains the strong battery diaphragm base fabric of hydrophily after sulfonation.
3）Sulfonation post-processes：Battery diaphragm base fabric after above-mentioned steps are handled is washed 2 times in 60 ~ 70% sulfuric acid, is washed
It is 5min to wash the time, then using 20 ~ 30% sulfuric acid scrubbing 2 times, wash time 7min, finally with deionized water rinse 3
Secondary, wash time 8.5min, 60min is dried at 95 DEG C, is plated at 85 DEG C, obtain the Ni-MH battery of graphene oxide modification every
Film.
Comparative example 5
The weight ratio of polyethylene fiber peacekeeping graphene oxide fiber is 3 in the present embodiment nickel-hydrogen battery separator fibrous material：1, skin
The mass ratio of layer and sandwich layer is 2：1, core layer length 15mm, fiber number 1.0tex, cortex length are 15mm, and fiber number is
1.2tex。
Preparation method：1）Wet method is hot-forming：Fibrous raw material is diluted, is discongested, disperses to prepare slurry, then through overly moist
Method is manufactured paper with pulp upper net forming, is finally modified by dehydration, heated-air drying, hot rolling and pressure-sizing and non-weaving cloth base fabric, hot-rolled temperature is made
For 110 DEG C, the hot rolling time is 15min, pressure 0.8kg/cm2。
2）Sulfonation is handled：Base fabric is put into sulfur trioxide sulfonation reactor, walk cloth speed 20m/min, it is warm in reactor
Spend for 38 DEG C, the concentration of sulfur trioxide is 93%, obtains the strong battery diaphragm base fabric of hydrophily after sulfonation.
3）Sulfonation post-processes：Battery diaphragm base fabric after above-mentioned steps are handled is washed 2 times in 60 ~ 70% sulfuric acid, is washed
It is 5min to wash the time, then using 20 ~ 30% sulfuric acid scrubbing 2 times, wash time 7min, finally with deionized water rinse 3
Secondary, wash time 8.5min, 60min is dried at 95 DEG C, is plated at 85 DEG C, obtain the Ni-MH battery of graphene oxide modification every
Film.
Nickel-metal hydride battery diaphragm material made from embodiment 1 ~ 8 and comparative example 1 ~ 5 is tested into its performance respectively, test method is such as
Under：
1）Diaphragm material is cut into 15cm × 1.5cm, the stretching that membrane is tested on HD 026N+ electronic fabric strength testers is broken
Resistance to spalling.
2）The test method of alkali absorbing rate：Diaphragm material is cut into 100mm × 100mm, weighs and is calculated as M1, is put into and fills matter
In the beaker for measuring the KOH solution that fraction is 30%, 1h is totally submerged, taking-up hangs on stent after 30min, weighs and be calculated as M2, inhales
Alkali content is calculated as follows：Alkali absorbing rate=M2/M1 × 100%.
3）Inhale the test method of alkali speed：Diaphragm material is cut into 150mm × 15mm, immerses the head end 5mm of long side
Mass fraction is the climb that lye after 30min is measured in 30% KOH solution.
4）The test method of percent thermal shrinkage：Diaphragm material is cut into 30mm × 10mm, is calculated as A1 × B1, by oven temperature
90 DEG C are arranged to, 1h is kept the temperature, then sample is put into baking oven, keeps the temperature 2h, then takes out membrane, sample is measured after cooling down 10min
The length A2 and width B2 of product, membrane longitudinal direction percent thermal shrinkage=（A1-A2）/ A1 × 100%, horizontal percent thermal shrinkage=（B1-B2）/B1
×100%。
Test result is shown in Table 1.
Diaphragm material the performance test results prepared by 1 embodiment 1 ~ 8 of table and comparative example 1 ~ 5
As shown in Table 1, the membrane stretch-proof fracture strength that prepared by the present invention reaches 168 ~ 180N/15mm, the intensity of diaphragm material
It is significantly improved；Alkali absorbing rate reaches 548 ~ 620%, inhales alkali 15 ~ 21cm/30min of speed, illustrates guarantor's fluidity of diaphragm material
Height, wellability is good, and vertical and horizontal percent thermal shrinkage substantially reduces, and reaches 1.9% and 1.2%, and the size for effectively increasing membrane is steady
It is qualitative；Compared with the diaphragm material that comparative example 1 is prepared using polyethylene and polypropylene composite materials fiber, mechanical strength, protect fluidity, leaching
Lubricant nature and dimensional stability all improve significantly.
The above described is only a preferred embodiment of the present invention, being not the limitation for making other forms to the present invention, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
Imitate embodiment.But it is every without departing from technical solution of the present invention content, the technical spirit according to the present invention is to above example institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection domain of technical solution of the present invention.
Claims (10)
1. a kind of graphene oxide is modified nickel-hydrogen battery separator, it is characterised in that：It is former by fiber of two-component skin-core structure fiber
Material is made, and two-component skin-core structure fiber includes cortex and sandwich layer, and the cortex is polyethylene fibre and graphene oxide fiber
Obtained composite fibre, wherein, the weight ratio of polyethylene fiber peacekeeping graphene oxide fiber is 2 ~ 5：1；The sandwich layer is poly- third
The mass ratio of alkene fiber, cortex and sandwich layer is 1 ~ 3：1.
2. graphene oxide according to claim 1 is modified nickel-hydrogen battery separator, it is characterised in that：The polyethylene fibre
Weight ratio with graphene oxide fiber is 3：1.
3. graphene oxide according to claim 1 is modified nickel-hydrogen battery separator, it is characterised in that：The cortex and sandwich layer
Mass ratio be 2：1.
4. graphene oxide according to claim 1 is modified nickel-hydrogen battery separator, it is characterised in that：The core layer length is
10 ~ 20mm, fiber number are 0.6 ~ 1.2tex, and cortex length is 10 ~ 20mm, and fiber number is 0.8 ~ 1.65tex.
5. graphene oxide according to claim 4 is modified nickel-hydrogen battery separator, it is characterised in that：The core layer length is
13 ~ 20mm, fiber number are 0.8 ~ 1.2tex, and cortex length is 13 ~ 18mm, and fiber number is 0.9 ~ 1.5tex.
6. claim 1-5 any one of them graphene oxide is modified the preparation method of nickel-hydrogen battery separator, it is characterised in that：
Comprise the following steps：
1）Wet method is hot-forming：Fibrous raw material is diluted, is discongested, it is scattered prepare slurry, then by wet method manufacture paper with pulp online into
Type, is finally made non-weaving cloth base fabric by dehydration, heated-air drying, hot rolling and pressure-sizing modification, and hot-rolled temperature is 120 ~ 140 DEG C,
The hot rolling time is 15 ~ 35min, and pressure is 1.0 ~ 3.0kg/cm2；
2）Sulfonation is handled：Base fabric is put into sulfur trioxide sulfonation reactor, walk cloth 12 ~ 18m/min of speed, reactor temperature
For 40 ~ 55 DEG C, the concentration of sulfur trioxide is 90 ~ 95%, obtains the strong battery diaphragm base fabric of hydrophily after sulfonation；
3）Sulfonation post-processes：Battery diaphragm base fabric after above-mentioned steps are handled is washed 1 ~ 2 time in 60 ~ 70% sulfuric acid, washing
Time is 4 ~ 6min, then using 20 ~ 30% sulfuric acid scrubbing 1 ~ 2 time, wash time is 5 ~ 8min, is finally floated with deionized water
Wash 2 ~ 3 times, wash time is 6 ~ 10min, and drying, plate, and obtains the nickel-hydrogen battery separator of graphene oxide modification.
7. graphene oxide according to claim 6 is modified the preparation method of nickel-hydrogen battery separator, it is characterised in that：It is described
Step 1）Middle hot-rolled temperature is 125 ~ 135 DEG C, and the hot rolling time is 20 ~ 30min, and pressure is 1.5 ~ 2.5kg/cm2。
8. graphene oxide according to claim 6 is modified the preparation method of nickel-hydrogen battery separator, it is characterised in that：Step
2）Described in sulfonation processing walk cloth speed be 16m/min, reactor temperature is 45 DEG C, and the concentration of sulfur trioxide is 93%.
9. graphene oxide according to claim 6 is modified the preparation method of nickel-hydrogen battery separator, it is characterised in that：Step
3）60 ~ 70% sulfuric acid scrubbing time is 5min in the sulfonation post processing, and 20 ~ 30% sulfuric acid scrubbing time is 7min, is gone
The time of ionized water rinsing is 8.5min.
10. graphene oxide according to claim 6 is modified the preparation method of nickel-hydrogen battery separator, it is characterised in that：Step
Rapid 3）Described in the temperature dried be 90 ~ 100 DEG C, the time of drying be 40 ~ 70min, and the temperature of pressing is 80 ~ 90 DEG C.
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| CN113235177A (en) * | 2021-05-24 | 2021-08-10 | 嘉兴市新丰特种纤维有限公司 | Preparation process and device of PP/PE low-melting-point composite fiber |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103700798A (en) * | 2013-12-16 | 2014-04-02 | 北京大学 | Fiber chemical energy storage power supply and preparation method thereof |
| JP2015531978A (en) * | 2012-09-14 | 2015-11-05 | フラウンホーファー・ゲゼルシャフト・ツール・フェルデルング・デア・アンゲヴァンテン・フォルシュング・エー・ファウ | Alkali metal-chalcogen battery with low self-discharge and high cycle life and high performance |
| CN105970605A (en) * | 2016-05-26 | 2016-09-28 | 厦门大学 | Graphene oxide composite non-woven fabric and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2015531978A (en) * | 2012-09-14 | 2015-11-05 | フラウンホーファー・ゲゼルシャフト・ツール・フェルデルング・デア・アンゲヴァンテン・フォルシュング・エー・ファウ | Alkali metal-chalcogen battery with low self-discharge and high cycle life and high performance |
| CN103700798A (en) * | 2013-12-16 | 2014-04-02 | 北京大学 | Fiber chemical energy storage power supply and preparation method thereof |
| CN105970605A (en) * | 2016-05-26 | 2016-09-28 | 厦门大学 | Graphene oxide composite non-woven fabric and preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113235177A (en) * | 2021-05-24 | 2021-08-10 | 嘉兴市新丰特种纤维有限公司 | Preparation process and device of PP/PE low-melting-point composite fiber |
| CN113235177B (en) * | 2021-05-24 | 2021-12-28 | 嘉兴市新丰特种纤维有限公司 | Preparation process and device of PP/PE low-melting-point composite fiber |
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