CN108539259A - Perfluor sodium polymer electrolyte and its preparation method and application and all-solid sodium ion battery and friction nanometer power generator system - Google Patents
Perfluor sodium polymer electrolyte and its preparation method and application and all-solid sodium ion battery and friction nanometer power generator system Download PDFInfo
- Publication number
- CN108539259A CN108539259A CN201710123721.5A CN201710123721A CN108539259A CN 108539259 A CN108539259 A CN 108539259A CN 201710123721 A CN201710123721 A CN 201710123721A CN 108539259 A CN108539259 A CN 108539259A
- Authority
- CN
- China
- Prior art keywords
- sodium
- solid
- perfluor
- polymer electrolyte
- power generator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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 relates to sodium-ion battery fields, disclose perfluor sodium polymer electrolyte and its preparation method and application and all-solid sodium ion battery and friction nanometer power generator system, and the method for preparing perfluor sodium polymer electrolyte includes：By perfluorinated sulfonic resin and contain Na+Solution carry out ion exchange.Contain aforementioned perfluor sodium polymer electrolyte in all-solid sodium ion battery provided by the invention, also, relative to the battery for using liquid electrolyte, all-solid sodium ion battery of the invention has excellent safety and higher energy density.
Description
Technical field
The present invention relates to sodium-ion battery fields, and in particular to a kind of method preparing perfluor sodium polymer electrolyte and
The perfluor sodium polymer electrolyte being prepared by this method and its application, a kind of a kind of all-solid sodium ion battery and friction are received
Rice generator system.
Background technology
Consumption with a large amount of fossil energies and being on the rise of pollution on the environment, it is also very desirable to develop new energy
Source technology replaces traditional fossil energy.
In recent years, the various principles of mechanical energy capture and antetype device are also reported successively, including electrostatic and friction effect,
Galvanomagnetic-effect and piezoelectric effect.
Particularly, professor Wang Zhonglin etc. has developed the friction nanometer generating based on friction effect and electrostatic induction coupling mechanism
Machine (TENGs).TENGs can be used for capturing various mechanical energy, for example, wind energy, raindrop energy and air stream energy.
But the energy of TENGs captures can not provide stable electric energy output, this is because the randomness of mechanical energy and
The pulse ac electric output characteristic of TENGs.Hence it is highly desirable to efficiently, the energy storage device stablized store friction nanometer generating
The electric energy of machine capture.
Large-scale electric energy storage request battery system not only has sufficiently high storage volume, and the system is also required to be into
This is efficient and environmentally friendly.
In recent years, it compared with lithium ion battery, due to the abundant natural resources of sodium and low cost, is answered as electric energy storage
With sodium-ion battery arouses widespread concern.
But sodium-ion battery still has huge challenge in terms of safety, service life and power density, limits biography
The commercialization of system sodium-ion battery (SIBs).
Therefore, in recent years the whole world all competitively carry out all-solid sodium ion battery research.
Invention content
An object of the present invention is to solve inflammable caused peace existing for the liquid electrolyte of all-solid sodium ion battery
The complete not high problem of property provides a kind of high security and can improve battery cycle life and improve the solid of energy density
Perfluor sodium polymer electrolyte, and the all-solid sodium ion battery containing the solid perfluor sodium polymer electrolyte.
The second object of the present invention is to solve the energy of existing friction nanometer power generator capture can not provide it is stable
The problem of electric energy exports, provides the energy storage device containing solid perfluor sodium polymer electrolyte to store friction nanometer power generator
The electric energy of capture, and realize electric energy output that is efficient and stablizing.
To achieve the goals above, in a first aspect, the present invention provides a kind of method preparing perfluor sodium polymer electrolyte,
Including：By perfluorinated sulfonic resin and contain Na+Solution carry out ion exchange.
Second aspect, the present invention is provided to be electrolysed by the perfluor sodium polymer that the method described in aforementioned first aspect is prepared
Matter.
The third aspect, the present invention provide the perfluor sodium polymer electrolyte described in aforementioned second aspect as all solid state sodium from
The application of the electrolyte of sub- battery.
Fourth aspect, the present invention provide a kind of all-solid sodium ion battery, including：
Solid electrolyte, the solid electrolyte are Na3P1-mAsmS4(0≤m≤0.5)、Na2O-11Al2O3、
Na3Zr2Si2PO12、Na3PSe4、94Na3PS4-6Na4SiS4、Na3SbS4、50Na2S-50P2S5、60Na2S-40GeS2、50Na2S-
50SiS2At least one of with perfluor sodium polymer electrolyte；And
Cathode.
5th aspect, the present invention provide a kind of friction nanometer power generator system, including complete solid described in aforementioned fourth aspect
State sodium-ion battery and friction nanometer power generator, the power storage that the friction nanometer power generator generates all solid state sodium from
In sub- battery.
All-solid sodium ion battery provided by the invention relative to use liquid electrolyte battery have excellent safety
Property and higher energy density.
All-solid sodium ion battery provided by the invention also has the advantages that with long service life, can be applied to portable electric
Sub- device can also act as electric vehicle power sources or in fixed energy-storage system, there is vast market prospect.
All-solid sodium ion battery provided by the invention can reduce the requirement to encapsulation.
Friction nanometer power generator system provided by the invention can store electric energy, and can realize that electric energy that is efficient and stablizing is defeated
Go out.
Friction nanometer power generator system provided by the invention also has the advantages that at low cost and environmental-friendly.
Description of the drawings
The test result of Fig. 1 PFSA-Na-1 films, wherein (a) is the folding for the PFSA-Na-1 films that embodiment 1 is prepared
State；(b) restore state for it；(c) stresses typical for the PFSA-Na-1 films being prepared for embodiment 1-strain stress relation is bent
Line；(d) it is the Arrhenius curve for the PFSA-Na-1 films being swollen in EC-PC in the mixed solvents.
Fig. 2 is the symmetrical Na of preparation example 3 | PFSA-Na | the test result of Na batteries, wherein (a) is the symmetrical of preparation example 3
Na | PFSA-Na | Na batteries electric current time history plot after applying 5 millivolts of DC voltages；(b) it is preparation example 3
Symmetrical Na | PFSA-Na | Na batteries are electroplated sodium/stripping sodium and test schematic diagram；(c) it is in 0.2mA/cm2Under current density, system
The symmetrical Na of standby example 3 | PFSA-Na | voltage versus time curve in sodium/stripping sodium experimentation is electroplated in Na batteries.
Fig. 3 be preparation example 3 all-solid-state battery test result, wherein (a) be different current densities under, preparation example 3
The charging and discharging curve of all-solid-state battery；(b) it is the high rate performance curve of the all-solid-state battery of preparation example 3；(c) it is 5mA/g's
Under current density, the long-term cycle performance of the all-solid-state battery of preparation example 3, capacity and coulombic efficiency are bent with the variation of cycle-index
Line；(d) it is the long-term cycle performance of the all-solid-state battery of preparation example 3 under the current density of 48mA/g, capacity and coulombic efficiency
With the change curve of cycle-index.
Fig. 4 is the test result of the friction nanometer power generator system of preparation example 5, wherein (a) is using the complete of preparation example 2
Solid state battery stores the schematic device of the pulse energy of the friction nanometer power generator system collection of preparation example 5；(b) it is preparation example
The partial enlarged view of 5 friction nanometer power generator system；(c) it is the open-circuit voltage of the friction nanometer power generator system of preparation example 5
Versus time curve；(d) it is the short circuit current versus time curve of the friction nanometer power generator system of preparation example 5；
(e) it is close in different electric currents to battery after the all-solid-state battery charging of preparation example 3 with the friction nanometer power generator system of preparation example 5
Discharge curve under degree.
Specific implementation mode
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
In a first aspect, the present invention provides a kind of methods preparing perfluor sodium polymer electrolyte, including：By perfluorinated sulfonic acid
Resin (PFSA) and contain Na+Solution carry out ion exchange.
It is described to contain Na+Solution for example can be sodium hydroxide solution, sodium acetate, sodium chloride solution and sodium nitrate solution
One or more of Deng.The present invention contains Na to described+The concentration of solution be not particularly limited.For example, described
Contain Na+Solution with Na+The molar concentration of meter can be 0.1~10mol/L.
By the ion exchange, by the proton exchange on PFSA at Na+, obtain PFSA-Na, as perfluor sodium polymerization
Object.
Preferably, the condition of the ion exchange includes：Temperature be 40~100 DEG C, the time be 6~for 24 hours.Described first connects
It touches PFSA can for example be immersed and contains Na+Solution in.
Preferably, this method further comprises：The product obtained after ion exchange is washed and dried successively.It is described
Water (such as deionized water etc.) progress may be used in washing.
Preferably, the condition of the drying includes：In the presence of protective gas, temperature be 5~45 DEG C, the time be 5 minutes extremely
1h.The protective gas for example can be at least one of helium, neon, argon gas and nitrogen.
Preferably, this method further includes：After carrying out the drying, in the presence of a molecular sieve, by the perfluor sodium after drying
Polymer dielectric is mixed with the mixed solvent containing ethylene carbonate and makrolon.Perfluor sodium polymer after drying
Electrolyte can realize swelling by the mixing, and perfluor sodium polymer electrolyte of the invention is provided to significantly facilitate
Ionic conductivity.
Preferably, the condition of the mixing includes：Temperature is 5~45 DEG C, and the time is 12~72h.
The present invention is not particularly limited the type of the molecular sieve, as long as being that by point of adsorption moisture effect
Son sieve.For example, the molecular sieve can beActive molecular sieve.The present invention is not special to the dosage of the molecular sieve
Limitation, those skilled in the art can according to function and effect and combine this field conventional amount used select.
Under preferable case, the EC's and PC of the in the mixed solvent containing ethylene carbonate (EC) and makrolon (PC)
Volume ratio is 1：(0.6~1.5).The present invention does not require the dosage of the mixed solvent particularly, as long as enabling to institute
It states the perfluor sodium polymer electrolyte after drying and is immersed in the in the mixed solvent.
Second aspect, the present invention provides the perfluor sodium polymer electricity being prepared by the method described in aforementioned first aspect
Xie Zhi.
The third aspect, the present invention provides the perfluor sodium polymer electrolyte described in aforementioned second aspect as all solid state sodium
The application of the electrolyte of ion battery.
Fourth aspect, the present invention provides a kind of all-solid sodium ion batteries, including：
Solid electrolyte, the solid electrolyte are Na3P1-mAsmS4(0≤m≤0.5)、Na2O-11Al2O3(β-three oxidations two
Aluminium), Na3Zr2Si2PO12、Na3PSe4、94Na3PS4-6Na4SiS4、Na3SbS4、50Na2S-50P2S5、60Na2S-40GeS2、
50Na2S-50SiS2At least one of with perfluor sodium polymer electrolyte；And
Cathode.
Preferably, the solid electrolyte is the perfluor sodium polymer electrolyte described in second aspect of the present invention.
The Na2O-11Al2O3As β-alundum (Al2O3) (Wen, Z.Y., Cao, J.D., Gu, Z.H., Xu, X.X.,
Zhang,F.L.Research on sodium sulphur battery for energy storage,Solid State
Ionics 2008,179,1697-1701)。
Under preferable case, is formed and contain P2- types Na in the anode sizing agent of the anode0.67NixMgyMn1-x-yO2(0≤x≤
0.5,0≤y≤0.2).Using containing P2- types Na0.67NixMgyMn1-x-yO2Material as anode sizing agent with the use of the present invention
Solid electrolyte formed energy storage device of the all-solid sodium ion battery as friction nanometer power generator system when, can be efficient
Store the energy that friction nanometer power generator generates.It was found by the inventors of the present invention that using other materials in the prior art, such as
Na3V2(PO4)3、NaMn0.44O2And NaFePO4When equal materials are as anode sizing agent, the energy of storage friction nanometer power generator generation
Ability performance it is general, only using containing P2- types Na0.67NixMgyMn1-x-yO2Material when storage capacity 60%.
Under preferable case, the P2- types Na0.67NixMgyMn1-x-yO2It is made using method comprising the following steps：
1) under the conditions of alkaline solution, sodium source and EDTA is dissolved in aqueous solution, the first solution is obtained；
2) first solution is mixed with manganese source, nickel source and magnesium source, obtains the second solution；
3) second solution is mixed with citric acid and/or ethylene glycol, obtains third solution；
4) the third solution is formed into gel, and is dried and roasts successively.
Preferably, the P2- types Na is being prepared0.67NixMgyMn1-x-yO2Method in, EDTA, citric acid and the P2-
Type Na0.67NixMgyMn1-x-yO2In total metal ion dosage molar ratio be 1：(1.05~2)：(0.6~1.2).
Preferably, the P2- types Na is being prepared0.67NixMgyMn1-x-yO2Method in, in step 3), by described second
When solution is mixed with citric acid and/or ethylene glycol, make the pH value of the third solution by the way that alkaline matter is added into solution
It is 5.5~6.8.
The alkaline matter of the present invention is preparing the P2- types Na such as can be ammonium hydroxide0.67NixMgyMn1-x-yO2
Method in, in step 1), the alkaline solution condition can also be formed by using ammonium hydroxide.
Preferably, the sodium source is at least one of sodium hydroxide, sodium chloride, sodium nitrate and sodium acetate.
Preferably, the manganese source is at least one of manganese nitrate, manganese chloride and manganese acetate.
Preferably, the nickel source is at least one of nickel nitrate, nickel chloride and nickel acetate.
Preferably, the magnesium source is at least one of magnesium nitrate, magnesium chloride and magnesium acetate.
Preferably, the sodium source, manganese source, nickel source and the dosage molar ratio in magnesium source are according to the P2- types
Na0.67NixMgyMn1-x-yO2Quantitative relation determine.
The present invention, which may be used, heats the third solution at 40~100 DEG C to form gel.
Under preferable case, the P2- types Na is being prepared0.67NixMgyMn1-x-yO2Method in, it is described dry in step 4)
Dry condition includes：Temperature is 80~160 DEG C, and the time is 6~48h.
Under preferable case, the P2- types Na is being prepared0.67NixMgyMn1-x-yO2Method in, in step 4), the roasting
The condition of burning includes：Temperature is 700~1200 DEG C, and the time is 4~36h.The roasting can carry out in air atmosphere.
Preferably, it is formed in the anode sizing agent of the anode and also contains acetylene black and Kynoar.
Under preferable case, in the anode sizing agent, the P2- types Na0.67NixMgyMn1-x-yO2With the acetylene black and
The content weight ratio of the Kynoar is (10~30)：(1.2~3)：1.
Under preferable case, the thickness of the solid electrolyte is 100nm~50 μm, more preferably 500nm~5 μm.Also
It is to say, the solid electrolyte of the invention can be film-form, or sheet.
Preferably, the cathode is metallic sodium and/or carbon material.
5th aspect, the present invention provides a kind of friction nanometer power generator system, including friction nanometer power generator and aforementioned
All-solid sodium ion battery described in fourth aspect, the power storage that the friction nanometer power generator generates is in all solid state sodium
In ion battery.
The friction nanometer power generator system of all-solid sodium ion battery containing the present invention can be by friction nanometer power generator
The power storage of generation, and can realize electric energy output that is efficient and stablizing.
The present invention is not particularly limited the method and structure for forming the friction nanometer power generator, and existing friction is received
Rice generator can use, and primary object of the invention is the provision of perfluor sodium polymer electrolyte and contains the perfluor
The all-solid sodium ion battery of sodium polymer electrolyte.Those skilled in the art apply the perfluor sodium polymer electricity containing the present invention
The all-solid-state battery of solution matter can be used in the energy of efficient storage friction nanometer power generator capture.
It below will the present invention will be described in detail by example.
In following instance, in case of no particular description, the various raw materials used are all from commercially available.
Preparation example 1：Prepare P2- types Na0.67Ni0.23Mg0.1Mn0.67O2
The molar ratio of ethylenediamine tetra-acetic acid (EDTA), citric acid and total metal ion is 1：1.5：1.By stoichiometric ratio
EDTA be dissolved in NH3·H2In O, and the heating stirring at 40 DEG C, then by the NaNO of calculation amount3It is added in above-mentioned solution.
Work as NaNO3After being completely dissolved, by the Mn (NO of calculation amount3)2·4H2O、Ni(NO3)2·6H2O and Mg (NO3)2·6H2O is dissolved in
In above-mentioned solution.After heating and stirring 10min, the citric acid of calculation amount is added, control citric acid adition process (uses
NH3·H2O adjust) pH value be about 6.Then the solution is stirred at 70 DEG C up to forming gel, then the drying at 120 DEG C
24h.Finally, the precursor obtained roasts 15h at 900 DEG C and obtains final product in air.It is spare.
Preparation example 2：Prepare P2- types Na0.67Ni0.42Mg0.2Mn0.38O2
This preparation example is carried out using method similar with preparation example 1, the difference is that the Mn (NO in this preparation example3)2·
4H2O、Ni(NO3)2·6H2O and Mg (NO3)2·6H2The dosage of O is different from preparation example 1, but according to the P2- of this preparation example
Type Na0.67Ni0.42Mg0.2Mn0.38O2Aforementioned substances are added in quantitative relation.Remaining is identical with preparation example 1.
Obtain P2- types Na0.67Ni0.42Mg0.2Mn0.38O2It is spare.
Embodiment 1：Prepare PFSA-Na-1
12h is impregnated at 80 DEG C in the NaOH aqueous solutions of 1M by ion-exchange, by perfluorinated sulfonic resin (PFSA)
It is converted into PFSA-Na-1.Then, it is washed with deionized, and dry in glove box Ar atmosphere at 25 DEG C.
The PFSA-Na-1 films flexible that the present embodiment is prepared are as shown in (a) and (b) in Fig. 1, wherein (a) is
The PFSA-Na-1 films of folded state；(b) it is the PFSA-Na-1 films of recovery state.
It is prepared using stretched plastic film method for testing performance (GBT13022-1991) test the present embodiment
The strain-stress relation of PFSA-Na-1 films obtains stresses typical-strain stress relation of PFSA-Na-1 films shown in (c) in Fig. 1
Curve.
Then PFSA-Na-1 films are immersed in the EC-PC (v of 60mL：V=1：1) in the mixed solvent, mixed solvent are contained in
One contains 20 gramsIn the closed container of active molecular sieve, 48h is preserved at 25 DEG C.
(d) in Fig. 1 is the Arrhenius curve for the PFSA-Na-1 films being swollen in EC-PC in the mixed solvents.
Embodiment 2：Prepare PFSA-Na-2
18h is impregnated at 60 DEG C in the NaOH aqueous solutions of 1M by ion-exchange, by perfluorinated sulfonic resin (PFSA)
It is converted into PFSA-Na-2.Then, it is washed with deionized, and dry in glove box Ar atmosphere at 30 DEG C.
The PFSA-Na-2 films that the present embodiment is prepared are similar to PFSA-Na-1 films flexible, and with it is flexible
Similar stresses typical-the strain curve of PFSA-Na-1 films.
Then PFSA-Na-2 films are immersed in the EC-PC (v of 60mL：V=1：1.2) in the mixed solvent, mixed solvent are held
Contain 20 grams at oneIn the closed container of active molecular sieve, 40h is preserved at 30 DEG C.
The Arrhenius curve of the PFSA-Na-2 films for the swelling that the present embodiment obtains and the swelling in embodiment 1
The Arrhenius curve of PFSA-Na-1 films is similar.
Preparation example 3：Prepare symmetrical Na | PFSA-Na | Na all-solid-state batteries
Symmetrical Na | PFSA-Na | Na batteries are assembled with button cell (R2032) in the glove box that argon gas is filled.
The P2- types Na that the anode sizing agent of all-solid-state battery is 85% by mass ratio0.67Ni0.23Mg0.1Mn0.67O2(preparation example 1
Obtain), 10% acetylene black and 5% Kynoar (PVDF) mix, positive slurries are coated on Al foils, in a vacuum
Dry 12h, is then cut into electrode slice, weighs spare at 120 DEG C.All-solid-state battery cathode is metal sodium foil, pair of this preparation example
Na | PFSA-Na | the electrolyte in Na all-solid-state batteries is referred to as the PFSA-Na-1 films for the swelling that embodiment 1 is prepared.
Battery is with 0.2mA/cm made from this preparation example2Current density it is enterprising in cell tester (LANDCT2001A)
Row constant current charge-discharge test, to measure sodium ion transport number.(a) in Fig. 2 shows the symmetrical Na of this preparation example | PFSA-Na |
Na batteries electric current time history plot after applying 5 millivolts of DC voltages.(b) in Fig. 2 shows this preparation
The symmetrical Na of example | PFSA-Na | Na batteries are electroplated sodium/stripping sodium and test schematic diagram.(c) in Fig. 2 is shown in 0.2mA/cm2
Under current density, the symmetrical Na of this preparation example | PFSA-Na | voltage is electroplated in sodium/stripping sodium experimentation at any time in Na batteries
Change curve.
(a) in Fig. 3 is shown under different current densities, the charging and discharging curve of the all-solid-state battery of this preparation example, electric current
Density is from 5mA/g to 384mA/g；(b) in Fig. 3 shows the high rate performance of the all-solid-state battery of this preparation example；In Fig. 3
(c) it shows under the current density of 5mA/g, the long-term cycle performance of the all-solid-state battery of this preparation example, capacity and coulomb effect
Rate with cycle-index change curve；(d) in Fig. 3 is shown under the current density of 48mA/g, this preparation example it is all solid state
The long-term cycle performance of battery, capacity and coulombic efficiency with cycle-index change curve.
Preparation example 4：Prepare symmetrical Na | PFSA-Na | Na all-solid-state batteries
This preparation example is carried out using method similar with preparation example 3, except that：
The P2- types Na that the anode sizing agent of this preparation example all-solid-state battery is 80% by mass ratio0.67Ni0.42Mg0.2Mn0.38O2
(acquisition of preparation example 2), 12% acetylene black and 8% Kynoar (PVDF) mix, and positive slurries are coated on Al foils,
Dry 12h at 120 DEG C, is then cut into electrode slice, weighs spare in vacuum.All-solid-state battery cathode is metal sodium foil, this preparation
The symmetrical Na of example | PFSA-Na | the electrolyte in Na batteries is the PFSA-Na-2 films for the swelling that embodiment 2 is prepared.
Battery is with 0.2mA/cm made from this preparation example2Current density it is enterprising in cell tester (LANDCT2001A)
Row constant current charge-discharge test, to measure sodium ion transport number.The symmetrical Na of this preparation example | PFSA-Na | Na batteries are applying one
Electric current time history plot is similar to (a) in Fig. 2 after 5 millivolts of DC voltages.The symmetrical Na of this preparation example | PFSA-
Na | Na batteries are in 0.2mA/cm2Under current density, be electroplated sodium/stripping sodium experimentation in voltage versus time curve with
(c) in Fig. 2 is similar.
Under different current densities (from 5mA/g to 384mA/g), the charging and discharging curve and figure of the all-solid-state battery of this preparation example
(a) in 3 is similar；The high rate performance of the all-solid-state battery of this preparation example is similar to the result that (b) in Fig. 3 is shown；In 5mA/g
Current density under, the long-term cycle performance of the all-solid-state battery of this preparation example, capacity and coulombic efficiency with cycle-index change
It is similar to (c) in Fig. 3 to change curve；Under the current density of 48mA/g, the long-term cyclicity of the all-solid-state battery of this preparation example
Can, capacity and coulombic efficiency are similar to (d) in Fig. 3 with the change curve of cycle-index.
Preparation example 5：Form friction nanometer power generator system
Using document：Zhu,G.,Chen,J.,Zhang,T.J.,Jing,Q.S.,Wang,Z.L.Radial-arrayed
rotary electrification for high performance triboelectric generator,
Nat.Commun.2014,5,3426. methods provided form friction nanometer power generator, and the friction nanometer generating of this preparation example
The energy storage device of machine system is the symmetrical Na that preparation example 3 is prepared | PFSA-Na | Na all-solid-state batteries.
The performance of friction nanometer power generator system passes through an electrometer (Keithley 6514) and the height in parallel of connecting
Output impedance electrometer (Keithley 6517) to test open-circuit voltage and short circuit current respectively.
(a) in Fig. 4 is the friction nanometer power generator system receipts that this preparation example is stored using the all-solid-state battery of preparation example 3
The schematic device of the pulse energy of collection；(b) in Fig. 4 is the partial enlargement of the friction nanometer power generator system of this preparation example
Figure；(c) in Fig. 4 is the open-circuit voltage versus time curve of friction nanometer power generator system；(d) in Fig. 4 is friction
The short circuit current versus time curve of nano generator system；(e) in Fig. 4 is the friction nanometer generating with this preparation example
Machine system is to discharge curve of the battery under different current densities after the all-solid-state battery charging of preparation example 3.
Preparation example 6：Form friction nanometer power generator system
This preparation example is used and is carried out with method as preparation example 5, the difference is that the friction nanometer generating in this preparation example
The energy storage device of machine system is the symmetrical Na that preparation example 4 is prepared | PFSA-Na | Na all-solid-state batteries.
The open-circuit voltage versus time curve of the friction nanometer power generator system of this preparation example and (c) phase in Fig. 4
Seemingly；The short circuit current versus time curve of the friction nanometer power generator system of this preparation example is similar to (d) in Fig. 4；With
Friction nanometer power generator system prepared by this preparation example is to battery after the all-solid-state battery charging of preparation example 4 in different current densities
Under discharge curve it is similar to (e) in Fig. 4.
It can be seen that by the above results of the present invention：The all-solid sodium ion battery prepared with the present invention program can be direct
It is combined with the friction nanometer power generator of pulse output characteristics, realizes the energy of efficient storage friction nanometer power generator system acquisition
Amount.Compared with the existing sodium-ion battery using liquid, have more with all-solid sodium ion battery prepared by the present invention program
Good safety and cycle performance.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In the skill of the present invention
In art conception range, technical scheme of the present invention can be carried out a variety of simple variants, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, belongs to
Protection scope of the present invention.
Claims (12)
1. a kind of method preparing perfluor sodium polymer electrolyte, including：By perfluorinated sulfonic resin and contain Na+Solution carry out
Ion exchange.
2. according to the method described in claim 1, wherein, the condition of the ion exchange includes：Temperature is 40~100 DEG C, when
Between for 6~for 24 hours.
3. method according to claim 1 or 2, wherein this method further comprises：The product that will be obtained after ion exchange
It is washed and is dried successively；Preferably,
The condition of the drying includes：In the presence of protective gas, temperature is 5~45 DEG C, and the time is 5 minutes to 1h.
4. according to the method described in claim 3, wherein, this method further includes：After carrying out the drying, exist in molecular sieve
Under, the perfluor sodium polymer electrolyte after drying is mixed with the mixed solvent containing ethylene carbonate and makrolon；
Preferably,
The condition of the mixing includes：Temperature is 5~45 DEG C, and the time is 12~72h.
5. the perfluor sodium polymer electrolyte being prepared by the method described in any one of claim 1-4.
6. the application of perfluor sodium polymer electrolyte described in claim 5 as the electrolyte of all-solid sodium ion battery.
7. a kind of all-solid sodium ion battery, including：
Anode,
Solid electrolyte, the solid electrolyte are Na3P1-mAsmS4(0≤m≤0.5)、Na2O-11Al2O3、Na3Zr2Si2PO12、
Na3PSe4、94Na3PS4-6Na4SiS4、Na3SbS4、50Na2S-50P2S5、60Na2S-40GeS2、50Na2S-50SiS2And perfluor
At least one of sodium polymer；Preferably, which is perfluor sodium polymer electrolyte；And
Cathode.
8. battery according to claim 7, wherein formed and contain P2- types in the anode sizing agent of the anode
Na0.67NixMgyMn1-x-yO2(0≤x≤0.5,0≤y≤0.2).
9. battery according to claim 8, wherein formed in the anode sizing agent of the anode and also contain acetylene black and gather inclined
Vinyl fluoride；Preferably,
In the anode sizing agent, the P2- types Na0.67NixMgyMn1-x-yO2With the acetylene black and the Kynoar
Content weight ratio is (10~30)：(1.2~3)：1.
10. according to the battery described in any one of claim 7-9, wherein the thickness of the solid electrolyte is 100nm~50
μm；Preferably 500nm~5 μm.
11. according to the battery described in any one of claim 7-10, wherein the cathode is metallic sodium and/or carbon material.
12. the all-solid sodium ion electricity described in any one of a kind of friction nanometer power generator system, including claim 7-13
Pond and friction nanometer power generator, the power storage that the friction nanometer power generator generates is in the all-solid sodium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710123721.5A CN108539259B (en) | 2017-03-03 | 2017-03-03 | Sodium perfluorofluoride polymer electrolyte, preparation method and application thereof, all-solid-state sodium ion battery and friction nano-generator system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710123721.5A CN108539259B (en) | 2017-03-03 | 2017-03-03 | Sodium perfluorofluoride polymer electrolyte, preparation method and application thereof, all-solid-state sodium ion battery and friction nano-generator system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108539259A true CN108539259A (en) | 2018-09-14 |
| CN108539259B CN108539259B (en) | 2020-10-13 |
Family
ID=63488658
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710123721.5A Active CN108539259B (en) | 2017-03-03 | 2017-03-03 | Sodium perfluorofluoride polymer electrolyte, preparation method and application thereof, all-solid-state sodium ion battery and friction nano-generator system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108539259B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110416627A (en) * | 2019-08-09 | 2019-11-05 | 西南大学 | A kind of PFSA-Na solid union electrolyte membrance and its preparation method and application |
| CN110690496A (en) * | 2019-10-24 | 2020-01-14 | 西南大学 | PFSA-K solid-state composite electrolyte membrane and preparation method and application thereof |
| CN114551970A (en) * | 2021-11-17 | 2022-05-27 | 万向一二三股份公司 | Self-charging type all-solid-state battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768236A (en) * | 2009-12-25 | 2010-07-07 | 山东东岳神舟新材料有限公司 | Perfluorinated ion exchange resin as well as preparation method and application thereof |
| CN104610569A (en) * | 2015-01-20 | 2015-05-13 | 浙江大学 | Novel sodium-sulfur battery and preparation method of separator of battery |
| CN105576229A (en) * | 2015-12-11 | 2016-05-11 | 中国电子科技集团公司第十八研究所 | Method for preparing multielement positive pole material for sodium-ion batteries |
-
2017
- 2017-03-03 CN CN201710123721.5A patent/CN108539259B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768236A (en) * | 2009-12-25 | 2010-07-07 | 山东东岳神舟新材料有限公司 | Perfluorinated ion exchange resin as well as preparation method and application thereof |
| CN104610569A (en) * | 2015-01-20 | 2015-05-13 | 浙江大学 | Novel sodium-sulfur battery and preparation method of separator of battery |
| CN105576229A (en) * | 2015-12-11 | 2016-05-11 | 中国电子科技集团公司第十八研究所 | Method for preparing multielement positive pole material for sodium-ion batteries |
Non-Patent Citations (4)
| Title |
|---|
| ABHIK BANERJEE等: "Na3SbS4 :A Solution Processable Sodium Superionic Conductor for All‐Solid‐State Sodium‐Ion Batteries", 《ANGEW.CHEM.INT.ED》 * |
| CHENGYING CAO等: "Nafion membranes as electrolyte and separator for sodium-ion battery", 《HYDROGEN ENERGY》 * |
| HUIDAN HOU等: "P2-Type Na0.67Ni0.23Mg0.1Mn0.67O2 as a High-Performance Cathode for a Sodium-Ion Battery", 《INORGANIC CHEMISTRY》 * |
| K.HEMALATHA等: "Improved electrochemical performance of Na0.67MnO2 through Ni and Mg substitution", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110416627A (en) * | 2019-08-09 | 2019-11-05 | 西南大学 | A kind of PFSA-Na solid union electrolyte membrance and its preparation method and application |
| CN110416627B (en) * | 2019-08-09 | 2021-03-16 | 西南大学 | PFSA-Na solid composite electrolyte membrane and preparation method and application thereof |
| CN110690496A (en) * | 2019-10-24 | 2020-01-14 | 西南大学 | PFSA-K solid-state composite electrolyte membrane and preparation method and application thereof |
| CN114551970A (en) * | 2021-11-17 | 2022-05-27 | 万向一二三股份公司 | Self-charging type all-solid-state battery |
| CN114551970B (en) * | 2021-11-17 | 2023-08-15 | 万向一二三股份公司 | Self-charging all-solid-state battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108539259B (en) | 2020-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106025200B (en) | A kind of preparation method and applications of N doping MXene cell negative electrode material | |
| CN107221716B (en) | Rechargeable aqueous zinc ion battery | |
| Zhang et al. | Water-soluble polyacrylic acid as a binder for sulfur cathode in lithium-sulfur battery | |
| CN101662021B (en) | Preparation methods of nano-coated positive electrode materials and secondary aluminium cell using nano-coated positive electrode materials | |
| CN105118972B (en) | Metal hydroxide coated carbon and sulfur lithium-sulfur battery positive electrode material, and preparation method and application thereof | |
| CN103682476B (en) | Battery | |
| CN109742475B (en) | Recycling method of waste lithium ion battery negative electrode material | |
| CN104466134B (en) | The preparation method of self-supporting graphene/carbon nano-tube hybrid foam support amino anthraquinones base polymer | |
| CN106920989B (en) | A kind of copper selenium compound is the sodium-ion battery of negative electrode material | |
| CN110176591A (en) | A kind of preparation method of water system zinc ion secondary cell and its anode based on organic electrode materials | |
| CN109037664A (en) | A kind of carbon-coated Mo of N doping2The preparation method of C/C functional composite material and its application in lithium-sulfur cell | |
| CN104300128A (en) | Integrated membrane electrode structure for lithium sulfur battery and preparation method thereof | |
| CN107528066A (en) | A kind of water system Zinc ion battery based on carbonyls positive electrode and preparation method thereof | |
| CN109994322A (en) | A kind of cell type supercapacitor and application thereof | |
| CN107069043B (en) | Lithium ion battery and preparation method thereof | |
| CN106816576B (en) | A kind of preparation method of anode material of lithium-ion battery and products thereof and application | |
| CN105449271B (en) | A kind of CuS is the aluminium ion secondary cell and its preparation process of anode | |
| CN103074007A (en) | Water-based adhesive used in silicon anode of lithium ion battery and preparation method of silicon anode | |
| CN103855401A (en) | Lithium ion battery positive pole piece as well as preparation method and lithium ion battery comprising pole piece | |
| CN105633327B (en) | A kind of TiS2For the aluminium ion secondary cell and its preparation process of anode | |
| CN108539259A (en) | Perfluor sodium polymer electrolyte and its preparation method and application and all-solid sodium ion battery and friction nanometer power generator system | |
| CN105322241A (en) | Aqueous ion-exchange cell | |
| CN104638236B (en) | A kind of preparation method of the polyaniline of hollow core-shell structure/sulphur composite | |
| Xie et al. | A High‐Performance Alginate Hydrogel Binder for Aqueous Zn− Ion Batteries | |
| CN107331830A (en) | A kind of anode composite of lithium-sulfur cell and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |