CN109037552A - A kind of preparation method of the diaphragm material for sodium-sulphur battery - Google Patents
A kind of preparation method of the diaphragm material for sodium-sulphur battery Download PDFInfo
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- CN109037552A CN109037552A CN201810889058.4A CN201810889058A CN109037552A CN 109037552 A CN109037552 A CN 109037552A CN 201810889058 A CN201810889058 A CN 201810889058A CN 109037552 A CN109037552 A CN 109037552A
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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
- H01M50/431—Inorganic 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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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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
- H01M50/463—Separators, membranes or diaphragms characterised by their shape
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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
Abstract
The present invention is a kind of preparation method of diaphragm material for sodium-sulphur battery.The preparation that this method passes through 3-D ordered multiporous polypyrrole, and using the zinc acetate and potassium hydroxide solution of Porous Polypyrrole and high concentration as raw material, biggish specific surface area, the nitrogen-containing functional group on polypyrrole surface and the oxygen-containing functional group of zinc oxide that the porous structure of obtained material can provide make effectively adsorb polysulfide, effectively inhibit " shuttle effect ", the strong electric conductivity of polypyrrole.The transmission speed of electronics and ion can be improved in the present invention, to improve the chemical property and cyclical stability of lithium-sulfur cell on the whole.
Description
Technical field
The invention belongs to technical field of chemical power, and in particular to a kind of sodium-sulphur battery nanometer diaphragm material and its preparation side
Method, especially a kind of sodium-sulphur battery zinc oxide/Porous Polypyrrole composite material and preparation method.
Background technique
Sodium-sulphur battery be U.S. Ford company in 1967 Invention Announce first.So far just more than 40 years history.Generally
In the case of battery be usually be made of several parts such as anode, cathode, electrolyte, diaphragm and shell.Generally conventional secondary cell is such as
Lead-acid battery, ickel-cadmium cell etc. are all made of solid electrode and liquid electrolyte, and sodium-sulphur battery is exactly the opposite, it is by melting
What the liquid electrode and solid electrolyte for melting state formed, general work temperature is 300-350 DEG C.Constitute the active material of its cathode
It is molten metal sodium, positive active material is liquid sulfur and sodium polysulfide fused salt.It is similar to lithium-sulfur cell, sulphur in sodium-sulphur battery
Theoretical specific capacity is 1675mAh g-1.At present in several countries for storing the electric power generated by wind-power electricity generation, photovoltaic devices, with
And conventional power plant.Moreover, sodium-sulphur battery will not generate exhaust emission, so being considered non-evergreen due to sealing when in use
Colour circle is protected, and almost all of battery material can recycle.In view of these advantages, seek alternative energy source at us
This epoch, sodium-sulphur battery are a valuable research directions.
But the high temperature sodium-sulphur battery still has many problems to need to solve.Firstly, battery must operate at high temperature, so that
Electrode material is kept molten by；Secondly because sodium is contacted with water can burn or explode, so abnormally dangerous；Third is put certainly
Electricity.Therefore, in order to which safety and performance consider, sealing appropriate is needed, can work at high temperature and not will crack.
But since the operation temperature of the high temperature sodium-sulphur battery is up to 300 DEG C, the danger such as explosion, corrosion are easily caused, and need to consume
A large amount of energy maintains its operation temperature, seriously limits its extensive use.Therefore people begin trying research room temperature sodium sulphur electricity
Pond.Room temperature sodium-sulphur batter was put forward for the first time in 2006 by the Hyo-JunAhn seminar of South Korea, and subsequent people begin to focus on and grind
Study carefully.However, since metallic sodium is more active than lithium, so the operation facing challenges ratio Li-S of Na-S battery at ambient temperature
Battery is more, especially in terms of the capacity holding during the utilization rate of sulphur active material and circulation.It is similar with lithium-sulfur cell, room
Warm sodium-sulphur battery is when using liquid electrolyte, because of the insulating properties of sulphur, polysulfide is soluble in electrolyte and leads to the effect that shuttles
It answers, the reasons such as volume expansion lead to low, poor circulation of the utilization rate of sulphur etc., so that the chemical property of sodium-sulphur battery receives
It seriously affects.
Summary of the invention
The purpose of the present invention is provide a kind of diaphragm material for sodium-sulphur battery for deficiency present in current techniques
Preparation method.The invention is using the zinc acetate and potassium hydroxide solution of Porous Polypyrrole and high concentration as raw material, obtained material
Porous structure biggish specific surface area, the nitrogen-containing functional group on polypyrrole surface and the oxygen-containing functional group of zinc oxide that can provide
Make effectively adsorb polysulfide, effectively inhibit " shuttle effect ", electronics and ion can be improved in the strong electric conductivity of polypyrrole
Transmission speed, to improve the chemical property and cyclical stability of lithium-sulfur cell on the whole.
Technical scheme is as follows:
A kind of preparation method of the diaphragm material for sodium-sulphur battery, this method comprises the following steps:
Step 1: monodispersed silicon dioxide microsphere is prepared；Positive second silester and dehydrated alcohol are mixed, solution is obtained
A；By ammonium hydroxide, dehydrated alcohol and deionized water mixing obtain solution B；Solution A and solution B are mixed again, after stirring 4~12h,
It is centrifuged and is put into the dry 36~48h of vacuum oven；Obtain monodispersed silicon dioxide microsphere；
Wherein, in solution A, volume ratio is positive second silester: dehydrated alcohol=1:5~15, in solution B, volume ratio ammonia
Water: dehydrated alcohol: deionized water=1:1~5:1~15；Volume ratio solution A: solution B=1:0.5~2；The ammonium hydroxide it is dense
Degree is 25~28wt.%；
Step 2: the preparation of silica template: add after upper step is obtained monodispersed silicon dioxide microsphere grinding
Enter into ethyl alcohol, is made into the suspension of 1-10wt%, ultrasonic disperse 2~24 hours, then stands at room temperature, after volatile dry,
It is put into Muffle furnace, 12~18h is calcined at 500~700 DEG C, obtains the silica ball template of marshalling；
Step 3: the preparation of 3-D ordered multiporous polypyrrole:
After 0~5 DEG C of mixed solution and 0~5 DEG C of ferric chloride solution are mixed, 0~5 DEG C at a temperature of react 8~12h,
Then it after solid being rinsed with clear water, is soaked in hydrofluoric acid solution 7-10 days, obtains Porous Polypyrrole；The concentration of hydrofluoric acid is
10~60wt.%；
Wherein, 0.3~0.5mM sodium acetate and 0.3~0.5mM pyrroles are contained in mixed solution, and every 10mL mixing is molten
Contain 0.3~2g of silica ball template in liquid；The concentration of ferric chloride solution is 0.3~0.5mM；Volume ratio mixed solution: chlorine
Change ferrous solution=2~5:2~5；
Step 4: zinc oxide/Porous Polypyrrole composite material is prepared:
Porous Polypyrrole is added in methanol, 3~5h of ultrasonic disperse, it is suspended to obtain Porous Polypyrrole at 40~55 DEG C
Liquid；Then the suspension of Porous Polypyrrole material is added in the methanol solution of zinc acetate, at 40~55 DEG C stir 20~
Then the methanol solution of potassium hydroxide is added dropwise in 60min thereto, stir 1~1.5h after being added dropwise at 40~55 DEG C, centrifugation is simultaneously
It is dry, obtain zinc oxide/Porous Polypyrrole composite material；
Wherein, in Porous Polypyrrole suspension, the Porous Polypyrrole of 2~3g is added in every 100~120mL methanol；Acetic acid
In the methanol solution of zinc, the zinc acetate of 2~6g is added in every 150~200mL methanol；In the methanol solution of potassium hydroxide, every 100
The potassium hydroxide of 0.5~2g is added in~120mL methanol；Volume ratio Porous Polypyrrole suspension: the methanol solution of zinc acetate: hydrogen
Methanol solution=10 of potassium oxide~12:15~20:10~12.
Step 5: preparing has zinc oxide/Porous Polypyrrole coating modified diaphragm；Zinc oxide obtained/porous is poly-
Pyrroles's composite material and conductive agent and binder are placed in mortar according to the ratio that mass ratio is 7~9: 0.5~2.5: 0.5~2.5
In, ground and mixed is at slurry, and by slurry blade coating on polypropylene, polyethylene film, coating thickness is 10~20 μm, 55~80 DEG C
Lower drying 10~for 24 hours, it is cut into thin slice using slitter, obtains that there is zinc oxide/Porous Polypyrrole coating modified diaphragm.
The above-mentioned preparation method with zinc oxide/Porous Polypyrrole coating modified diaphragm for sodium-sulphur battery, wherein
Involved raw material are commercially available, and equipment used and technique are known to those skilled in the art
's.
In the present invention in order to sodium-sulphur battery there are the problem of, template is done by silica and has prepared Porous Polypyrrole,
By further synthesizing to obtain zinc oxide/Porous Polypyrrole composite material, it is applied to polypropylene, polyethylene film surface conduct
Diaphragm.Firstly, polypyrrole can significantly shorten the transmission path of ion as conducting polymer, it is anti-to improve sodium-sulphur battery electrochemistry
Answer activity；Secondly as Porous Polypyrrole have huge specific surface area, can effectively adsorb generated in charge and discharge process it is more
Sulfide prevents polysulfide to be dissolved into electrolyte, improves the utilization rate of active material；Again, zinc oxide is uniformly distributed in
When Porous Polypyrrole surface, since the oxygen-containing functional group of zinc oxide has extremely strong absorption property, it can be further improved more sulphur
The absorption of compound inhibits " shuttle effect ".And the lighter weight of Porous Polypyrrole, the entirety that will not influence sodium-sulphur battery are close
Degree.
Compared with prior art, the method for the present invention has substantive distinguishing features outstanding as follows:
1, polypyrrole has stronger conductive capability as conducting polymer, and active material sulphur is that electric conductivity is very poor,
Therefore the electric conductivity that common diaphragm surface helps to improve active matter as sodium-sulphur battery diaphragm is coated on using polypyrrole, thus
Improve the utilization rate and battery capacity of active material.
2, Porous Polypyrrole is due to making it have huge specific surface area with a large amount of holes, and polypyrrole itself contains
There is a large amount of nitrogen-containing functional group, this is all to be conducive to its adsorption energy to the polysulfide generated in sodium-sulphur battery charge and discharge process
Power inhibits it to be dissolved in electrolyte and generates " shuttle effect ".
3, zinc oxide is due to that can reinforce the suction-operated to polysulfide, further suppress and " wear with oxygen-containing functional group
Shuttle effect " improves sodium-sulphur battery cycle performance.
Compared with 104610569 A of prior art CN, zinc oxide/Porous Polypyrrole composite wood involved in the present invention
Material, be primarily due to the porous structure of polypyrrole and the nano-scale of Zinc oxide particles, have great specific surface area, this for
Adsorbing polysulfide has extremely strong effect.Secondly, there are nitrogen-containing functional group abundant, the O of Zinc oxide particles in polypyrrole surface2-?
With extremely strong adsorptivity, these all make zinc oxide/Porous Polypyrrole have extremely strong more sulphur as sodium-sulphur battery composite material
Compound absorption property.Again, for Porous Polypyrrole as a kind of conducting polymer, electric conductivity is outstanding, is conducive to reduce battery
Internal impedance improves the efficiency of transmission of electronics and ion, so that the utilization rate of active material is improved, to improve battery capacity
And cyclical stability.And in 104610569 A of prior art CN, polysulfide is adsorbed by addition sodium ion exchange resin
Ability it is limited, and need to add polyethylene glycol oxide to reduce cell resistance, further reduce the sodium of absorption polysulfide from
Specific gravity shared by sub-exchange resin further limits absorption of the 104610569 A septation of prior art CN to polysulfide
Ability.Therefore, obtained electrochemical results show outstanding cycle performance in the present invention, and first time discharge capacity is
1400mAh g-1, after 100 circulations, capacity still can achieve 930mAh g-1, and it is poly- with uncoated zinc oxide/porous
The sodium-sulphur battery of the blank diaphragm of pyrroles's composite material then shows very poor cycle performance, and discharge capacity is for the first time
1280mAh g-1, 170mAh g is decayed to after recycling 100 times-1Left and right.And it discharges for the first time in 104610569 A of prior art CN
Capacity is only 700mAh-1Left and right, after 100 circulations, capacity is only 590mAh-1Left and right.
In short, the modified diaphragm coated with zinc oxide/Porous Polypyrrole that the present invention prepares, the electric conductivity of polypyrrole
It is higher, it may advantageously facilitate the transmission of electronics and ion, improve the utilization rate of active material, the porous structure of polypyrrole provides huge
The common adsorption reaction of the suction-operated of the oxygen-containing functional group of bigger serface, the nitrogen-containing functional group of polypyrrole and zinc oxide generates
Polysulfide, inhibition " shuttle effect " are a kind of pole to improve the capacity of sodium-sulphur battery, high rate performance and cycle performance
Has the modified diaphragm of market prospects.
Detailed description of the invention
Fig. 1 is zinc oxide/Porous Polypyrrole composite material X-ray diffractogram prepared by embodiment 1.
Fig. 2 is zinc oxide/Porous Polypyrrole composite material scanning electron microscope diagram prepared by embodiment 1.
Fig. 3 is zinc oxide/Porous Polypyrrole composite material prepared by embodiment 1 as sodium-sulphur battery diaphragm material and sky
Cyclic curve when white diaphragm is as diaphragm in the case where current density is 0.1C.
Specific embodiment
Embodiment 1
The first step prepares monodispersed silicon dioxide microsphere:
Positive second silester and ethanol solution are mixed according to the volume ratio of 1:5.In addition, being by concentration
The ammonium hydroxide of 25wt.%, dehydrated alcohol and deionized water are mixed by the volume ratio of 1:2:2.By two groups of solution according to 1:0.5
Ratio mix, after magnetic stirrer 4h, be centrifuged and be put into the dry 36h of vacuum oven, obtain averagely straight
Diameter is the silicon dioxide microsphere of 300nm.
Second step, the preparation of silica template:
Take the SiO of 1000mg prepared2Ball grind into powder is placed in a beaker with the solution that ethyl alcohol is made into 5wt%, right
It carries out ultrasound, makes SiO2Microballoon is evenly dispersed in ethanol, then stands it at room temperature, after volatile dry that gained is white
Color precipitating is put into magnetic boat, is put into Muffle furnace and is calcined 12h at 500 DEG C, obtains the SiO of marshalling2Template.
Third step, the preparation of 3-D ordered multiporous polypyrrole:
It weighs 1000mg silica ball template to be put into 200mL beaker, 20mL is then added thereto and contains 0.3mM second
Mixed solution is put into refrigerator and stands at 5 DEG C by the solution of sour sodium and 0.3mM pyrroles.Then configuration concentration is the chlorine of 0.3mM
Change ferrous solution be also placed in refrigerator 5 DEG C at a temperature of stand.After standing 2h, measures 20mL ferric chloride solution and be added to titanium dioxide
Silicon, pyrroles, sodium acetate mixed solution in, obtained final mixed solution is put into refrigerator and is reacted at a temperature of 5 DEG C
12h.The hydrofluoric acid that concentration is 20wt.% is soaked in after finally silica surface is rinsed out without the polypyrrole of pattern with clear water
10 days removal SiO of etching dissolution in solution2Template obtains Porous Polypyrrole.
4th step prepares zinc oxide/Porous Polypyrrole composite material:
Porous Polypyrrole material suspension is prepared first, weighs the Porous Polypyrrole of 2g, is added in 100mL methanol, is put
Enter and carry out ultrasound in ultrasonic machine, ultrasonic time 3h, temperature is 50 DEG C, forms suspension.Then the zinc acetate of 5.72g is weighed,
It is added in 150mL methanol.The potassium hydroxide for weighing 1.508g is added in 100mL methanol.The two is stirred respectively,
Wherein, mixing time is 40min, and whipping temp is 50 DEG C.The suspension of Porous Polypyrrole material is finally added to second
In the methanol solution of sour zinc, 60min is stirred, whipping temp is 50 DEG C.The methanol solution of potassium hydroxide is added dropwise to zinc acetate
In the mixing methanol solution of Porous Polypyrrole material, 1.5h is stirred after dropwise addition, whipping temp is 50 DEG C, is centrifuged after reaction
And it is dry.Zinc oxide content in gained zinc oxide/Porous Polypyrrole composite material is 46.7%, and the prior art is mostly 40%
Below.
5th step, preparing has zinc oxide/Porous Polypyrrole coating modified diaphragm:
It according to mass ratio is 8: 1: 1 by zinc oxide obtained/Porous Polypyrrole composite material and conductive agent and binder
Ratio is placed in mortar, and ground and mixed uniformly scratches on polyethylene film at slurry, by slurry, coating thickness be 15 μm, 60
Dry 12h, is cut into thin slice using slitter at DEG C, obtains having zinc oxide/Porous Polypyrrole coating modified diaphragm.
6th step, the preparation of battery anode slice and the assembling of battery:
Sulphur and graphene are put in mortar according to the mass ratio of 2:1 after being put into reaction kettle after grinding 1h and are put into stove
12h is heated at 155 DEG C.It is again 8: 1: 1 according to mass ratio by obtained sulphur/graphene composite material and conductive agent and binder
Ratio be placed in mortar, ground and mixed uniformly scratches on carbon containing aluminium foil at slurry, by slurry, at 60 DEG C it is dry for 24 hours, use
Tablet press machine pushes flakiness in 5MPa pressure, obtains positive plate.It is anode, metal Li piece as cathode, oxygen using gained sulphur/graphene
The modified diaphragm for changing the coating of zinc/Porous Polypyrrole is diaphragm and to coat zinc oxide/Porous Polypyrrole one side opposite with positive plate,
Electrolyte is added, battery assembly is carried out in glove box, obtains button with modified diaphragm CR2025 half-cell.And with gained
Sulphur/graphene is anode, metal Li piece is cathode, blank diaphragm is diaphragm, and electrolyte is added, battery pack is carried out in glove box
Dress is obtained with blank diaphragm button CR2025 half-cell.
Chemical property analysis (BTS-5V5mA, new prestige) is carried out to prepared sample.
Fig. 1 is zinc oxide/Porous Polypyrrole composite material X-ray diffractogram prepared by embodiment 1.It can be with from figure
Find out there is one than wider peak in 26 ° of place, this peak is the peak of polypyrrole.And remaining peak with the peak of zinc oxide
It is corresponding, to demonstrate the successful synthesis of zinc oxide/Porous Polypyrrole composite material.
Fig. 2 is zinc oxide/Porous Polypyrrole composite material scanning electron microscope diagram prepared by embodiment 1.It can see
To obtained polypyrrole surface it is uniform sequential be dispersed with average diameter be 300nm circular hole, zinc oxide due to size compared with
It is small to observe.
Fig. 3 be embodiment 1 prepared by zinc oxide/Porous Polypyrrole modified diaphragm as sodium-sulphur battery diaphragm when in electric current
Density is the cyclic curve under 0.1C.The sodium-sulphur battery that zinc oxide/Porous Polypyrrole modified diaphragm makees diaphragm discharges for the first time to be held
Amount is 1400mAh g-1, after 100 circulations, capacity still can achieve 930mAh g-1, it is steady to be demonstrated by outstanding circulation
It is qualitative.And the battery of blank diaphragm assembly is used to show it due to not having zinc oxide/Porous Polypyrrole interlayer, chemical property
First discharge specific capacity is only 1280mAh g-1, since serious " shuttle effect " and electric conductivity are bad, capacity attenuation is fast
Speed, after only recycling 4 times, capacity just decays to 215mAh g-1。
Embodiment 2
, with embodiment 1, difference is the body of the positive second silester of the first step and ethanol solution according to 1:10 for other
Product ratio mixes.In addition, dehydrated alcohol and deionized water are mixed by the volume ratio of 1:3:3 by concentrated ammonia liquor.By two
Group solution mixes, and after magnetic stirrer 4h, is centrifuged and is put into the dry 36h of vacuum oven.Gained is porous poly-
Pyrroles's pore-size distribution is reduced in 330nm or so, specific surface area, and adsorption capacity is declined, and zinc oxide content is reduced to 43.1%,
Coated on diaphragm and after carrying out battery assembly, discharge capacity is 1360mAh g to gained electrochemical data for the first time-1, after recycling 100 times
Gained specific discharge capacity is 881mAh g-1。
Embodiment 3
, with embodiment 1, difference is the body of the positive second silester of the first step and ethanol solution according to 1:15 for other
Product ratio mixes.In addition, dehydrated alcohol and deionized water are mixed by the volume ratio of 1:5:5 by concentrated ammonia liquor.By two
Group solution mixes, and after magnetic stirrer 4h, is centrifuged and is put into the dry 36h of vacuum oven.Gained is porous poly-
Pyrroles's pore-size distribution is reduced in 380nm or so, specific surface area, and adsorption capacity is declined, and zinc oxide content is reduced to 39.8%,
Coated on diaphragm and after carrying out battery assembly, discharge capacity is 1390mAh g to gained electrochemical data for the first time-1, after recycling 100 times
Gained specific discharge capacity is 850mAh g-1。
Unaccomplished matter of the present invention is well-known technique.
Claims (2)
1. a kind of preparation method of the diaphragm material for sodium-sulphur battery, it is characterized in that this method comprises the following steps:
Step 1: monodispersed silicon dioxide microsphere is prepared；Positive second silester and dehydrated alcohol are mixed, solution A is obtained；It will
Ammonium hydroxide, dehydrated alcohol and deionized water mixing, obtain solution B；Solution A and solution B are mixed again, after stirring 4~12h, centrifugation
And it is put into the dry 36~48h of vacuum oven；Obtain monodispersed silicon dioxide microsphere；
Wherein, in solution A, volume ratio is positive second silester: dehydrated alcohol=1:5~15, in solution B, volume ratio ammonium hydroxide: nothing
Water-ethanol: deionized water=1:1~5:1~15；Volume ratio solution A: solution B=1:0.5~2；The concentration of the ammonium hydroxide is
25~28wt.%；
Step 2: it the preparation of silica template: is added to after upper step is obtained monodispersed silicon dioxide microsphere grinding
In ethyl alcohol, it is made into the suspension of 1-10wt%, ultrasonic disperse 2~24 hours, then stands, after volatile dry, is put at room temperature
In Muffle furnace, 12~18h is calcined at 500~700 DEG C, obtains the silica ball template of marshalling；
Step 3: the preparation of 3-D ordered multiporous polypyrrole:
After 0~5 DEG C of mixed solution and 0~5 DEG C of ferric chloride solution are mixed, in 0~5 DEG C of at a temperature of 8~12h of reaction, then
After solid is rinsed with clear water, it is soaked in hydrofluoric acid solution 7-10 days, obtains Porous Polypyrrole；The concentration of hydrofluoric acid be 10~
60wt.%；
Wherein, 0.3~0.5mM sodium acetate and 0.3~0.5mM pyrroles are contained in mixed solution, and in every 10mL mixed solution
Contain 0.3~2g of silica ball template；The concentration of ferric chloride solution is 0.3~0.5mM；Volume ratio mixed solution: iron chloride
Solution=2~5:2~5；
Step 4: zinc oxide/Porous Polypyrrole composite material is prepared:
Porous Polypyrrole is added in methanol, 3~5h of ultrasonic disperse at 40~55 DEG C obtains Porous Polypyrrole suspension；So
The suspension of Porous Polypyrrole material is added in the methanol solution of zinc acetate afterwards, 20~60min is stirred at 40~55 DEG C, so
The methanol solution of potassium hydroxide is added dropwise thereto afterwards, stirs 1~1.5h after being added dropwise at 40~55 DEG C, is centrifuged and dry, obtains
To zinc oxide/Porous Polypyrrole composite material；
Wherein, in Porous Polypyrrole suspension, the Porous Polypyrrole of 2~3g is added in every 100~120mL methanol；Zinc acetate
In methanol solution, the zinc acetate of 2~6g is added in every 150~200mL methanol；In the methanol solution of potassium hydroxide, every 100~
The potassium hydroxide of 0.5~2g is added in 120mL methanol；Volume ratio Porous Polypyrrole suspension: the methanol solution of zinc acetate: hydrogen-oxygen
Change methanol solution=10~12:15~20:10~12 of potassium.
2. the preparation method for the diaphragm material of sodium-sulphur battery as described in claim 1, it is characterized in that further including step 5:
Preparing has zinc oxide/Porous Polypyrrole coating modified diaphragm；By zinc oxide obtained/Porous Polypyrrole composite material with lead
Electric agent and binder are placed in mortar according to the ratio that mass ratio is 7~9: 0.5~2.5: 0.5~2.5, and ground and mixed is slurried
Material, by slurry blade coating on polypropylene, polyethylene film, coating thickness is dry 10 at 10~20 μm, 55~80 DEG C~for 24 hours,
It is cut into thin slice using slitter, obtains that there is zinc oxide/Porous Polypyrrole coating modified diaphragm.
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Cited By (5)
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| CN110034292A (en) * | 2019-04-30 | 2019-07-19 | 河北工业大学 | A kind of 3-D ordered multiporous polypyrrole/zinc oxide lithium ion battery negative material and preparation method |
| CN110247008A (en) * | 2019-06-28 | 2019-09-17 | 浙江大学 | A kind of preparation method and low temperature sodium-sulphur battery of low temperature sodium sulphur battery diaphragm |
| CN110504403A (en) * | 2019-07-18 | 2019-11-26 | 肇庆市华师大光电产业研究院 | A kind of preparation method of the ZIF8/ zinc oxide composite for lithium-sulfur cell functionality interlayer |
| CN114824658A (en) * | 2022-04-29 | 2022-07-29 | 渤海大学 | Preparation method of honeycomb porous flaky nickel oxide material diaphragm for potassium-oxygen battery |
| CN115602997A (en) * | 2022-10-13 | 2023-01-13 | 河北工业大学（Cn） | Co 3 O 4 -PVA-PPy-PP diaphragm, preparation method and application thereof, and lithium-sulfur battery containing diaphragm |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102130323A (en) * | 2011-02-12 | 2011-07-20 | 中南大学 | Lithium ion battery film cathode containing porous polymer elastomer and preparation method thereof |
| CN103490027A (en) * | 2013-08-12 | 2014-01-01 | 中国科学院化学研究所 | Membrane for lithium-sulfur battery and preparation method of membrane |
| CN103700820A (en) * | 2014-01-07 | 2014-04-02 | 中国科学院化学研究所 | Lithium ion selenium battery with long service life |
| CN104350631A (en) * | 2012-04-10 | 2015-02-11 | 加州理工学院 | Novel separators for electrochemical systems |
| CN104638215A (en) * | 2013-08-21 | 2015-05-20 | 通用汽车环球科技运作有限责任公司 | Flexible membranes and coated electrodes for lithium based batteries |
| CN105140447A (en) * | 2015-07-23 | 2015-12-09 | 中国科学院上海硅酸盐研究所 | Functional composite membrane for lithium-sulfur battery and preparation method of functional composite membrane |
| US20180034059A1 (en) * | 2015-02-13 | 2018-02-01 | The Regents Of The University Of California | Coated sulfur particle electrode and method |
| CN107863508A (en) * | 2017-10-23 | 2018-03-30 | 合肥国轩高科动力能源有限公司 | A kind of porous selenium composite positive pole of polypyrrole cladding and preparation method thereof |
| CN108321369A (en) * | 2017-12-28 | 2018-07-24 | 肇庆市华师大光电产业研究院 | A kind of macropore carbon/zinc oxide/sulphur composite material and preparation method can be used for lithium-sulfur cell and application |
-
2018
- 2018-08-07 CN CN201810889058.4A patent/CN109037552B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102130323A (en) * | 2011-02-12 | 2011-07-20 | 中南大学 | Lithium ion battery film cathode containing porous polymer elastomer and preparation method thereof |
| CN104350631A (en) * | 2012-04-10 | 2015-02-11 | 加州理工学院 | Novel separators for electrochemical systems |
| CN103490027A (en) * | 2013-08-12 | 2014-01-01 | 中国科学院化学研究所 | Membrane for lithium-sulfur battery and preparation method of membrane |
| CN104638215A (en) * | 2013-08-21 | 2015-05-20 | 通用汽车环球科技运作有限责任公司 | Flexible membranes and coated electrodes for lithium based batteries |
| CN103700820A (en) * | 2014-01-07 | 2014-04-02 | 中国科学院化学研究所 | Lithium ion selenium battery with long service life |
| US20180034059A1 (en) * | 2015-02-13 | 2018-02-01 | The Regents Of The University Of California | Coated sulfur particle electrode and method |
| CN105140447A (en) * | 2015-07-23 | 2015-12-09 | 中国科学院上海硅酸盐研究所 | Functional composite membrane for lithium-sulfur battery and preparation method of functional composite membrane |
| CN107863508A (en) * | 2017-10-23 | 2018-03-30 | 合肥国轩高科动力能源有限公司 | A kind of porous selenium composite positive pole of polypyrrole cladding and preparation method thereof |
| CN108321369A (en) * | 2017-12-28 | 2018-07-24 | 肇庆市华师大光电产业研究院 | A kind of macropore carbon/zinc oxide/sulphur composite material and preparation method can be used for lithium-sulfur cell and application |
Non-Patent Citations (1)
| Title |
|---|
| HAIPENG LI ETC: "Three-dimensionally ordered hierarchically porous polypyrrole loading sulfur as high-performance cathode for lithium/sulfur batteries", 《POLYMER》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110034292A (en) * | 2019-04-30 | 2019-07-19 | 河北工业大学 | A kind of 3-D ordered multiporous polypyrrole/zinc oxide lithium ion battery negative material and preparation method |
| CN110034292B (en) * | 2019-04-30 | 2022-05-24 | 河北工业大学 | Three-dimensional ordered porous polypyrrole/zinc oxide lithium ion battery negative electrode material and preparation method thereof |
| CN110247008A (en) * | 2019-06-28 | 2019-09-17 | 浙江大学 | A kind of preparation method and low temperature sodium-sulphur battery of low temperature sodium sulphur battery diaphragm |
| CN110247008B (en) * | 2019-06-28 | 2020-05-22 | 浙江大学 | Preparation method of low-temperature sodium-sulfur battery diaphragm and low-temperature sodium-sulfur battery |
| CN110504403A (en) * | 2019-07-18 | 2019-11-26 | 肇庆市华师大光电产业研究院 | A kind of preparation method of the ZIF8/ zinc oxide composite for lithium-sulfur cell functionality interlayer |
| CN110504403B (en) * | 2019-07-18 | 2022-03-15 | 肇庆市华师大光电产业研究院 | Preparation method of ZIF 8/zinc oxide composite material for functional interlayer of lithium-sulfur battery |
| CN114824658A (en) * | 2022-04-29 | 2022-07-29 | 渤海大学 | Preparation method of honeycomb porous flaky nickel oxide material diaphragm for potassium-oxygen battery |
| CN114824658B (en) * | 2022-04-29 | 2023-06-27 | 渤海大学 | Preparation method of honeycomb porous sheet nickel oxide material diaphragm for potassium-oxygen battery |
| CN115602997A (en) * | 2022-10-13 | 2023-01-13 | 河北工业大学（Cn） | Co 3 O 4 -PVA-PPy-PP diaphragm, preparation method and application thereof, and lithium-sulfur battery containing diaphragm |
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