CN108808129A - A kind of preparation method of gel electrolyte for water system sodium-ion battery - Google Patents
A kind of preparation method of gel electrolyte for water system sodium-ion battery Download PDFInfo
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- CN108808129A CN108808129A CN201810687331.5A CN201810687331A CN108808129A CN 108808129 A CN108808129 A CN 108808129A CN 201810687331 A CN201810687331 A CN 201810687331A CN 108808129 A CN108808129 A CN 108808129A
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- ion battery
- water system
- electrostatic spinning
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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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
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
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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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- Secondary Cells (AREA)
Abstract
The invention belongs to technical field of material chemistry, are related to a kind of preparation method of the gel-form solid polymer electrolyte for water system sodium-ion battery.This method includes three steps of preparation of the preparation of electrostatic spinning precursor liquid, the preparation of electrostatic spinning PAN fiber film and gel polymer electrolyte, obtain that there is very abundant reticular structure pattern using electrostatic spinning process, and have the characteristics that electrochemical stability height, nonflammable PAN fiber film, the phenomenon that being applied to lithium battery anode after activated, zinc dendrite can effectively be avoided to pierce through diaphragm occurs.
Description
Technical field
The present invention relates to a kind of electrolyte technologies of preparing of battery, more particularly, to one kind for water system sodium ion electricity
The preparation method of the gel-form solid polymer electrolyte in pond, belongs to technical field of material chemistry.
Background technology
Water system sodium-ion battery has the characteristics that high safety, pollution-free, inexpensive and long-life, disclosure satisfy that extensive storage
Can system requirement, as regenerative resource (luminous energy and wind energy etc.) develop and use and intelligent grid structure key technology it
One, it increasingly attracts attention with industrialization to its research.Water system sodium-ion battery has been opened by fast development in recent years
Send out a series of positive and negative anodes electrode materials for having height ratio capacity and high circulation stability；By design to battery system with it is excellent
Change, also achieves achievement in manufacturing cost improving energy density and reducing, industrialization has begun to take shape.Although the battery
The research and development of technology and industrialization time are also very short, are also faced with lot of challenges.
As a kind of new battery system, water system sodium-ion battery is with production cost is low, has a safety feature, is environmentally protective
The features such as, it is received more and more attention in the research and development of battery.2012, Whitacre etc. reported a kind of activated carbon and makees
For cathode, λ-MnO2As the water system sodium-ion battery of anode, with higher specific capacity, but in the building-up process of anode
In use electrolytic oxidation manganese as raw material so that contain Mn in product2O3Equal impurity, can cause the chemical property of battery
It influences, and cost is higher, it is difficult to meet practical demand.Such as：106784756 A of CN disclose it is a kind of for water system sodium from
The preparation method of sub- battery anode composite material is prepared by the method using zinc as cathode, and NMO-RGO composite materials are just
Pole, sodium salt and zinc salt mixed solution are the novel water system sodium-ion battery of electrolyte to be had by the compound RGO in preparation process
The conductivity of the raising composite material of effect, and the battery prepared is green safe.But it will produce zinc in the long process of battery
The growth of dendrite, zinc dendrite can pierce through diaphragm, and battery is made to generate short circuit.
Safety problem is caused using the leakage of liquid electrolyte in water system sodium-ion battery.With to security requirement
Raising, polymer dielectric is widely studied as the substitute of liquid system.Gel polymer electrolyte is by polymer
Formed with liquid electrolyte, not only remain the good machining property of polymer, also with liquid electrolyte it is high from
Electron conductivity can serve as electrolyte and play the role of diaphragm, have a good application prospect, gel polymer electrolyte
Matter can also have successfully been isolated the electrode in battery and liquid leakage is made to minimize.
Invention content
The purpose of the present invention is to provide a kind of gel polymer electrolytes for sodium-ion battery anode.The gel is poly-
Polymer electrolyte is to use polyacrylonitrile（PAN）Fiber is obtained as presoma using electrostatic spinning process.
Include the following steps provided by the present invention for the method for preparing gel polymer electrolyte of sodium-ion battery：
（1）The preparation of electrostatic spinning precursor liquid：
By polyacrylonitrile powder and n,N-Dimethylformamide according to 1:1 ~ 9 mass ratio mixing, is stirred after sealing at 50 ~ 80 DEG C
20 ~ 30h is mixed, transparent uniform solution is obtained；
（2）The preparation of electrostatic spinning PAN fiber film：
It takes 5 ~ 10mL electrostatic spinnings precursor liquid in syringe, syringe is fixed on micro pump, start electrostatic spinning processing,
Voltage is 15 ~ 25kV, and it is 15 ~ 30cm to receive distance, and rotating speed is 500 ~ 1000r/min；
（3）The preparation of gel polymer electrolyte：Take step（2）In PAN fiber film in Na2SO4And ZnSO4Mass concentration is
1：0.5h ~ 1h is infiltrated in 1 mixed electrolyte, obtains gel polymer electrolyte.
The above-mentioned method for preparing gel polymer electrolyte for sodium-ion battery, wherein involved raw material are equal
It is commercially available, equipment used is known to those skilled in the art.
Compared with prior art, the invention has the advantages that and advantageous effect：
The preparation process of PAN fiber film is simple, and technique is intuitive, at low cost, and prepared PAN fiber film has very abundant net
Shape structure and morphology, and have the characteristics that electrochemical stability is high, nonflammable.PAN fiber film passes through Na2SO4And ZnSO4It is mixed
It closes after being activated in electrolyte, gel polymer electrolyte both has the good machining property of polymer, also has liquid electric
Solve the high ionic conductivity of matter.Water system sodium-ion battery will produce zinc dendrite in long-term work, and the growth of zinc dendrite can pierce through
The phenomenon that diaphragm makes battery that short circuit occur, and gel polymer electrolyte can effectively avoid zinc dendrite from piercing through diaphragm occurs.
Description of the drawings
Fig. 1 is the scanning electron microscope of the PAN fiber film obtained by embodiment 1（SEM）Figure.
Fig. 2 is embodiment 1-3（In descending order）Charge and discharge of the obtained gel polymer electrolyte at 4 C are bent
Line chart.
Specific implementation mode
The invention will be further described with specific implementation mode with reference to the accompanying drawings of the specification.
Embodiment 1：
The first step prepares electrostatic spinning precursor liquid：
PAN powder and DMF solution are pressed 1:9 mass ratio mixing, after sealing is placed in 65 DEG C of waters bath with thermostatic control mechanical agitation for 24 hours
Obtain electrospun solution.
Second step prepares PAN fiber film：
It takes the PAN/DMF solution of 8mL in syringe, the syringe with PAN/DMF solution is fixed on micro pump, metering needle
The distance between point and receiving barrel start motor to distance 25cm is set, and set rotating speed 1000r/min, open high
Voltage source is simultaneously adjusted to the voltage 15kV set, examines whether spinning carries out.After spinning for 24 hours, high-voltage electrostatic spinning dress is closed
It sets, obtains the tunica fibrosa of PAN, Fig. 1 is the scanning electron microscope result of gained PAN fiber film, it can be seen that prepared PAN fiber film
With very abundant reticular structure pattern.
Third walks, and prepares gel polymer electrolyte：
By PAN fiber film obtained in Na2SO4And ZnSO4Mass concentration is 1：0.5h is infiltrated in 1 mixed electrolyte, you can
To gel polymer electrolyte.
Embodiment 2：
The first step prepares electrostatic spinning precursor liquid：
PAN powder and DMF solution are pressed 1:1 mass ratio mixing, after sealing is placed in 50 DEG C of waters bath with thermostatic control mechanical agitation for 24 hours
Obtain electrospun solution.
Second step prepares PAN fiber film：
It takes the PAN/DMF solution of 8mL in syringe, the syringe with PAN/DMF solution is fixed on micro pump, metering needle
The distance between point and receiving barrel start motor to distance 25cm is set, and set rotating speed 1000r/min, open high
Voltage source is simultaneously adjusted to the voltage 15kV set, examines whether spinning carries out.After spinning for 24 hours, high-voltage electrostatic spinning dress is closed
It sets, obtains the tunica fibrosa of PAN.
Third walks, and prepares gel polymer electrolyte：
By PAN fiber film obtained in Na2SO4And ZnSO4Mass concentration is 1：0.5h is infiltrated in 1 mixed electrolyte, you can
To gel polymer electrolyte.
Embodiment 3:
The first step prepares electrostatic spinning precursor liquid：
PAN powder and DMF solution are pressed 1:9 mass ratio mixing, after sealing is placed in 65 DEG C of waters bath with thermostatic control mechanical agitation for 24 hours
Obtain electrospun solution.
Second step prepares PAN fiber film：
It takes the PAN/DMF solution of 8mL in syringe, the syringe with PAN/DMF solution is fixed on micro pump, metering needle
The distance between point and receiving barrel start motor to distance 20cm is set, and set rotating speed 800r/min, open high pressure
Power supply is simultaneously adjusted to the voltage 25kV set, examines whether spinning carries out.After spinning for 24 hours, high-voltage electrostatic spinning device is closed,
Obtain the tunica fibrosa of PAN.
Third walks, and prepares gel polymer electrolyte：
By PAN fiber film obtained in Na2SO4And ZnSO4Mass concentration is 1：0.5h is infiltrated in 1 mixed electrolyte, you can
To gel polymer electrolyte, Fig. 2 gives is being applied to lithium battery just by the gel polymer electrolyte obtained by embodiment 1-3
After extremely, the curve graph of the progress charge and discharge electro-detection at 4 C, as a result showing all has good charge-discharge performance.
Embodiment 4：
The first step prepares electrostatic spinning precursor liquid：
PAN powder and DMF solution are pressed 1:9 mass ratio mixing, after sealing is placed in 65 DEG C of waters bath with thermostatic control mechanical agitation for 24 hours
Obtain electrospun solution.
Second step prepares PAN fiber film：
It takes the PAN/DMF solution of 8mL in syringe, the syringe with PAN/DMF solution is fixed on micro pump, metering needle
The distance between point and receiving barrel start motor to distance 25cm is set, and set rotating speed 1000r/min, open high
Voltage source is simultaneously adjusted to the voltage 15kV set, examines whether spinning carries out.After spinning for 24 hours, high-voltage electrostatic spinning dress is closed
It sets, obtains the tunica fibrosa of PAN.
Third walks, and prepares gel polymer electrolyte：
By PAN fiber film obtained in Na2SO4And ZnSO4Mass concentration is 1：0.5h is infiltrated in 1 mixed electrolyte, you can
To gel polymer electrolyte.
Unaccomplished matter of the present invention is known technology.
Claims (6)
1. a kind of preparation method of gel electrolyte for water system sodium-ion battery, which is characterized in that including（1）Electrostatic spinning
The preparation of precursor liquid,（2）The preparation of electrostatic spinning PAN fiber film and（3）Three steps of preparation of gel polymer electrolyte.
2. the preparation method of the gel electrolyte according to claim 1 for water system sodium-ion battery, which is characterized in that
Described（1）The preparation method of electrostatic spinning precursor liquid is：Polyacrylonitrile powder is mixed into sealing with n,N-Dimethylformamide
Afterwards, 20 ~ 30h is stirred at 50 ~ 80 DEG C, obtains transparent uniform solution.
3. the preparation method of the gel electrolyte according to claim 2 for water system sodium-ion battery, which is characterized in that
The polyacrylonitrile powder is 1 with n,N-Dimethylformamide mass ratio:1~9.
4. the preparation method of the gel electrolyte according to claim 1 for water system sodium-ion battery, which is characterized in that
Described（2）The preparation method of electrostatic spinning PAN fiber film is：Take 5 ~ 10mL steps（1）In electrostatic spinning precursor liquid obtained
In syringe, syringe is fixed on micro pump, starts electrostatic spinning processing, voltage is 15 ~ 25kV, and it is 15 to receive distance
~ 30cm, rotating speed are 500 ~ 1000r/min.
5. the preparation method of the gel electrolyte according to claim 1 for water system sodium-ion battery, which is characterized in that
Described（3）Method for preparing gel polymer electrolyte is：Take step（2）In PAN fiber film in Na2SO4And ZnSO4's
0.5h ~ 1h is infiltrated in mixed electrolyte, obtains gel polymer electrolyte.
6. the preparation method of the gel electrolyte according to claim 5 for water system sodium-ion battery, which is characterized in that
The Na2SO4And ZnSO4Mass ratio is 1：1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810687331.5A CN108808129A (en) | 2018-06-28 | 2018-06-28 | A kind of preparation method of gel electrolyte for water system sodium-ion battery |
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| CN201810687331.5A CN108808129A (en) | 2018-06-28 | 2018-06-28 | A kind of preparation method of gel electrolyte for water system sodium-ion battery |
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| CN108808129A true CN108808129A (en) | 2018-11-13 |
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| CN201810687331.5A Withdrawn CN108808129A (en) | 2018-06-28 | 2018-06-28 | A kind of preparation method of gel electrolyte for water system sodium-ion battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110512306A (en) * | 2019-08-20 | 2019-11-29 | 成都新柯力化工科技有限公司 | A kind of preparation method for the dielectric film inhibiting solid state lithium battery lithium dendrite growth |
| CN111224171A (en) * | 2019-12-12 | 2020-06-02 | 中国科学院大连化学物理研究所 | Water-based high-voltage electrolyte, and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102255106A (en) * | 2011-04-29 | 2011-11-23 | 哈尔滨工业大学 | PAMPSLi fiber based polymer electrolyte membrane preparation method utilizing electrospinning method |
| CN103715449A (en) * | 2012-10-09 | 2014-04-09 | 丰田自动车株式会社 | Sodium ion battery system |
| CN107732180A (en) * | 2017-09-27 | 2018-02-23 | 肇庆市华师大光电产业研究院 | A kind of preparation method for water system sodium-ion battery anode composite material |
| CN107959049A (en) * | 2017-11-23 | 2018-04-24 | 南开大学 | Preparation method, gel electrolyte and the lithium ion battery of gel electrolyte |
-
2018
- 2018-06-28 CN CN201810687331.5A patent/CN108808129A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102255106A (en) * | 2011-04-29 | 2011-11-23 | 哈尔滨工业大学 | PAMPSLi fiber based polymer electrolyte membrane preparation method utilizing electrospinning method |
| CN103715449A (en) * | 2012-10-09 | 2014-04-09 | 丰田自动车株式会社 | Sodium ion battery system |
| CN107732180A (en) * | 2017-09-27 | 2018-02-23 | 肇庆市华师大光电产业研究院 | A kind of preparation method for water system sodium-ion battery anode composite material |
| CN107959049A (en) * | 2017-11-23 | 2018-04-24 | 南开大学 | Preparation method, gel electrolyte and the lithium ion battery of gel electrolyte |
Non-Patent Citations (2)
| Title |
|---|
| K. VIGNAROOBAN ET AL.: "poly-acrylonitrile-based gel-polymer electrolytes for sodium-ion batteries", 《IONICS》 * |
| PRIYA CAROL ET AL.: "preparation and characterization of electrospun poly(acrylonitrile) fibrous membrane based gel polymer electrolytes for lithium-ion batteries", 《JOURNAL OF POWER SOURCES》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110512306A (en) * | 2019-08-20 | 2019-11-29 | 成都新柯力化工科技有限公司 | A kind of preparation method for the dielectric film inhibiting solid state lithium battery lithium dendrite growth |
| CN111224171A (en) * | 2019-12-12 | 2020-06-02 | 中国科学院大连化学物理研究所 | Water-based high-voltage electrolyte, and preparation method and application thereof |
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Application publication date: 20181113 |
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