CN110416627A - A kind of PFSA-Na solid union electrolyte membrance and its preparation method and application - Google Patents
A kind of PFSA-Na solid union electrolyte membrance and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of PFSA-Na solid union electrolyte membrances and its preparation method and application, belong to battery material technical field, the preparation method of the diaphragm is main are as follows: prepares PFSA-Na powder by ion-exchange reactions using PFSA-Li powder and sodium source as raw material first, then PFSA-Na glue is obtained after PFSA-Na powder being dissolved in organic solvent, electrolyte is added into the glue under stiring, obtain mixed solution, it is dry after finally mixed solution is scratched, PFSA-Na solid union electrolyte membrance is made.The membrane thicknesses prepared in this way are thinner, are conducive to the thickness that battery is thinned in commercialization process, promote energy density, which is used in secondary solid-state sodium-ion battery, the cyclical stability of the battery can be effectively improved.In addition, still can work normally with the battery that the diaphragm is assembled into subzero ten several years.This method is simple to operation, low for equipment requirements, is suitble to expanded production.
Description
Technical field
The invention belongs to battery material technical fields, and in particular to a kind of PFSA-Na solid union electrolyte membrance and its
Preparation method and application.
Background technique
Rechargeable battery is the basic motive technology of electric car and power grid energy storage, and the popularization and application of the technology not only may be used
To reduce fossil fuel using pollution on the environment, and can to avoid the intermittence of the green energy resources such as wind energy, solar energy,
Convenience is provided for the life and development of human society.Therefore, there is an urgent need to explore and find one kind to supplement existing high-energy
The energy-storage system of density, long circulation life lithium ion battery (LIBs).In recent years, since lithium resource earth reserves are small, lead to lithium
Ion battery cost is continuously improved.Sodium and lithium are located at same main group in the periodic table of elements, and sodium-ion battery and lithium ion battery have
Have identical electrochemical behavior, and sodium earth rich reserves are low in cost so that sodium-ion battery become most prospect lithium from
Sub- battery replacer.
In recent years due to lithium ion battery explosion and bring safety accident and casualties time it is commonplace, it is basic
The reason is that organic electrolyte used in traditional liquid battery has thermal instability, volatile, height is inflammable, in circulating battery
Electrochemical decomposition can occur in the process leads to cell expansion, serious to will cause leakage and then cause explosion accident on fire.Sodium from
Sub- battery is identical as lithium ion battery, is equally faced with organic electrolyte bring security risk, therefore use solid electrolyte
It is imperative instead of organic electrolyte.
Summary of the invention
In view of this, one of the objects of the present invention is to provide a kind of preparations of PFSA-Na solid union electrolyte membrance
Method；The second purpose is to provide a kind of PFSA-Na solid union electrolyte membrance；The third purpose is that providing PFSA-Na consolidates
Application of the state composite electrolyte diaphragm in secondary solid-state sodium-ion battery.
In order to achieve the above objectives, the invention provides the following technical scheme:
1, a kind of preparation method of PFSA-Na solid union electrolyte membrance, the method are as follows:
PFSA-Li powder is added to the water mixing together with sodium source, 5-24h is stirred at 40-150 DEG C, then through being centrifuged
Washing, drying, obtain PFSA-Na powder, obtain PFSA-Na glue after the PFSA-Na powder is then dissolved in organic solvent
Electrolyte is added in liquid into the PFSA-Na glue under stiring, obtains mixed solution, finally carries out the mixed solution
12-48h is dried after blade coating at 60-150 DEG C, PFSA-Na solid union electrolyte membrance is made.
Preferably, the PFSA-Li powder and the mass ratio of sodium source are 1-100:1-400.
Preferably, the mass fraction of PFSA-Na powder is 20-40% in the PFSA-Na glue；The PFSA-Na glue
The volume ratio of liquid and electrolyte is 0.5-200:1；The concentration of the electrolyte is 1mol/L.
Preferably, the sodium source is one of sodium chloride, sodium acetate, sodium nitrate, sodium hydroxide or sodium carbonate.
Preferably, the centrifuge washing is specially under the speed of 5000-9000r/min with deionized water centrifuge washing 3-
10 times, each centrifuge washing 3-5min.
Preferably, the drying is specially to dry 5-96h at 30-150 DEG C.
Preferably, the organic solvent be N,N-Dimethylformamide, N-Methyl pyrrolidone, acetonitrile, tetrahydrofuran or
One of dimethyl sulfoxide.
Preferably, solute is sodium perchlorate, sodium hexafluoro phosphate, trifluoromethanesulfonic acid sodium or bis trifluoromethyl in the electrolyte
One of sulfimide sodium, solvent is one of EC/DEC, EC/PC, DGM or DME in the electrolyte.
2, the PFSA-Na solid union electrolyte membrance of method preparation.
3, application of the PFSA-Na solid union electrolyte membrance in secondary solid-state sodium-ion battery.
The beneficial effects of the present invention are: the present invention provides a kind of PFSA-Na solid union electrolyte membrance and its systems
PFSA- is made by ion-exchange reactions first using PFSA-Li powder and sodium source as raw material in this method in Preparation Method and application
Then PFSA-Na powder is dissolved in acquisition PFSA-Na powder glue in organic solvent, electricity is added into the glue by Na powder
Solution liquid can control most by rationally controlling the volume ratio of the mass fraction of PFSA-Na powder, glue and electrolyte in glue
End form at mixed solution viscosity, guarantee the later period by blade coating formed solid union electrolyte membrance thickness；Pass through control
Temperature and time dry after the type and blade coating of solute and solvent, on the one hand can use specific in electrolyte in electrolyte processed
Solute improves the free sodium ions content in the solid union electrolyte membrance finally prepared, so that ionic conductivity is improved,
On the other hand, can use specific solvent in electrolyte reduces the crystallization of macromolecule matrix (PFSA) during the drying and film forming process
Degree to improve the chatter of its molecule segment, and then improves ionic conductivity.It wherein, can if drying temperature is excessively high after blade coating
Cause electrolyte to generate the adverse effects such as pyrolytic, cause free sodium in the solid union electrolyte membrance finally prepared from
Sub- content cannot improve, and drying time is too short, then drying can be made not exclusively to influence the solid union electrolyte finally prepared
The toughness of diaphragm.It is thinner with the membrane thicknesses of the method preparation in the present invention, be conducive to the thickness that battery is thinned in commercialization process
Degree promotes energy density, which is used in secondary solid-state sodium-ion battery, the stable circulation of the battery can be effectively improved
Property.In addition, still can work normally with the battery that the diaphragm is assembled into subzero ten several years.This method is simple to operation, right
Equipment requirement is low, is suitble to expanded production.
Other advantages, target and feature of the invention will be illustrated in the following description to a certain extent, and
And to a certain extent, based on will be apparent to those skilled in the art to investigating hereafter, Huo Zheke
To be instructed from the practice of the present invention.Target of the invention and other advantages can be realized by following specification and
It obtains.
Detailed description of the invention
To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention is made below in conjunction with attached drawing excellent
The detailed description of choosing, in which:
Fig. 1 is the shape appearance figure of the PFSA-Na solid union electrolyte membrance prepared in embodiment 1；
Fig. 2 is the PFSA-Na solid union electrolyte membrance prepared in embodiment 1 and prepares in comparative example 1 pure
The ionic conductivity test result figure of PFSA-Na solid electrolyte diaphragm；(a is that the PFSA-Na prepared in embodiment 1 consolidates in Fig. 2
The ionic conductivity test result of state composite electrolyte diaphragm, b is the pure PFSA-Na solid-state prepared in comparative example 1 in Fig. 2
The ionic conductivity test result of electrolyte membrance)
Fig. 3 is the ionic conductivity test result figure of the PFSA-Na solid union electrolyte membrance prepared in embodiment 2；
Fig. 4 is the ionic conductivity test result figure of the PFSA-Na solid union electrolyte membrance prepared in embodiment 3；
Fig. 5 is the ionic conductivity test result figure of the PFSA-Na solid union electrolyte membrance prepared in embodiment 4；
Fig. 6 is the PFSA-Na solid union electrolyte in embodiment 6 by preparing in the positive plate of the C of@containing NVP, embodiment 1
The electrochemical property test result figure of the sodium-ion battery of diaphragm composition；(a is charge and discharge of the battery in cyclic process in Fig. 6
Curve graph, b is the cycle performance of battery figure in Fig. 6)
Fig. 7 is the PFSA-Na solid union electrolyte in embodiment 6 by preparing in the positive plate of the C of@containing NFP, embodiment 1
The electrochemical property test result figure of the sodium-ion battery of diaphragm composition；(a is charge and discharge of the battery in cyclic process in Fig. 7
Curve graph, b is the cycle performance of battery figure in Fig. 7)；
Fig. 8 is the PFSA-Na solid union electrolyte in embodiment 6 by preparing in the positive plate of the C of@containing NMVP, embodiment 1
The electrochemical property test result figure of the sodium-ion battery of diaphragm composition；(a is charge and discharge of the battery in cyclic process in Fig. 8
Curve graph, b is the cycle performance of battery figure in Fig. 8)；
Fig. 9 is to be electrolysed in embodiment 6 by the positive plate containing HQ-NaFe, the PFSA-Na solid union for preparing in embodiment 1
The electrochemical property test result figure of the sodium-ion battery of matter diaphragm composition；(a is charge and discharge of the battery in cyclic process in Fig. 9
Electric curve graph, b is the cycle performance of battery figure in Fig. 9)；
Figure 10 be embodiment 7 in based on PFSA-Na solid union electrolyte membrance assembling sodium-ion battery at low temperature
Operational capability test result figure.
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
Embodiment 1
Prepare PFSA-Na solid union electrolyte membrance
PFSA-Li powder is added to the water mixing together with sodium hydroxide in mass ratio 1:150, stirs 5h at 50 DEG C,
Then with deionized water centrifuge washing 3 times under the speed of 9000r/min, each centrifuge washing 5min then dries at 120 DEG C
Dry 96h, obtains PFSA-Na powder, obtains PFSA-Na glue after which is dissolved in dimethyl sulfoxide, presses
The volume ratio of PFSA-Na glue and electrolyte is 40:1, and electrolyte is added into the PFSA-Na glue under stiring, is mixed
Solution is closed, dries 48h after finally being scratched the mixed solution at 80 DEG C, the PFSA-Na solid-state with a thickness of 20 μm is made
Composite electrolyte diaphragm, wherein the mass fraction of PFSA-Na powder is 20% in PFSA-Na glue, and solute is height in electrolyte
Sodium chlorate, solvent EC/DEC, the concentration of electrolyte are 1mol/L.The pattern of the PFSA-Na solid union electrolyte membrance is such as
Shown in Fig. 1.
Embodiment 2
Prepare PFSA-Na solid union electrolyte membrance
PFSA-Li powder is added to the water mixing together with sodium carbonate in mass ratio 1:400,10h is stirred at 80 DEG C, so
Afterwards with deionized water centrifuge washing 10 times under the speed of 7000r/min, each centrifuge washing 3min then dries at 150 DEG C
Dry 5h, obtains PFSA-Na powder, PFSA-Na glue is obtained after which is dissolved in acetonitrile, by PFSA-Na glue
Volume ratio with electrolyte is 200:1, and electrolyte is added into the PFSA-Na glue under stiring, obtains mixed solution, finally
12h is dried after the mixed solution is scratched at 150 DEG C, the PFSA-Na solid union electrolyte with a thickness of 40 μm is made
Diaphragm, wherein the mass fraction of PFSA-Na powder is 40% in PFSA-Na glue, and solute is sodium hexafluoro phosphate in electrolyte,
Solvent is DME, and the concentration of electrolyte is 1mol/L.
Embodiment 3
Prepare PFSA-Na solid union electrolyte membrance
PFSA-Li powder is added to the water mixing together with sodium chloride in mass ratio 100:1, is stirred at 150 DEG C for 24 hours,
Then with deionized water centrifuge washing 7 times under the speed of 5000r/min, each centrifuge washing 3min then dries at 60 DEG C
Dry 36h, obtains PFSA-Na powder, obtains PFSA-Na glue after which is dissolved in N-Methyl pyrrolidone, presses
The volume ratio of PFSA-Na glue and electrolyte is 0.5:1, and electrolyte is added into the PFSA-Na glue under stiring, is mixed
Solution is closed, dries 36h after finally being scratched the mixed solution at 60 DEG C, the PFSA-Na solid-state with a thickness of 20 μm is made
Composite electrolyte diaphragm, wherein the mass fraction of PFSA-Na powder is 20% in PFSA-Na glue, and solute is three in electrolyte
Fluorine methanesulfonic sodium, solvent EC/PC, the concentration of electrolyte are 1mol/L.
Embodiment 4
Prepare PFSA-Na solid union electrolyte membrance
PFSA-Li powder is added to the water mixing together with sodium nitrate in mass ratio 80:1,2h is stirred at 120 DEG C, so
Afterwards with deionized water centrifuge washing 5 times under the speed of 6000r/min, each centrifuge washing 4min is then dried at 30 DEG C
48h obtains PFSA-Na powder, PFSA-Na glue is obtained after which is dissolved in tetrahydrofuran, by PFSA-Na
The volume ratio of glue and electrolyte is 100:1, and electrolyte is added into the PFSA-Na glue under stiring, obtains mixed solution,
For 24 hours, the PFSA-Na solid union electricity with a thickness of 30 μm is made in drying at 100 DEG C after finally the mixed solution is scratched
Solve matter diaphragm, wherein the mass fraction of PFSA-Na powder is 30% in PFSA-Na glue, and solute is double fluoroforms in electrolyte
Base sulfimide sodium, solvent DGM, the concentration of electrolyte are 1mol/L.
Comparative example 1
The difference from embodiment 1 is that obtaining PFSA-Na glue after PFSA-Na powder is dissolved in dimethyl sulfoxide, directly
It connects and dries 48h after being scratched PFSA-Na glue at 80 DEG C, pure PFSA-Na solid electrolyte diaphragm is made.
Embodiment 5
(1) it is prepared in the PFSA-Na solid union electrolyte membrance and comparative example 1 prepared in testing example 1
The ionic conductivity of pure PFSA-Na solid electrolyte diaphragm
It prepares the PFSA-Na solid union electrolyte membrance prepared in embodiment 1 and in comparative example 1 pure
PFSA-Na solid electrolyte diaphragm is clipped in respectively between two stainless steel electrodes, CR2032 type battery is assembled into respectively, in room temperature
The lower test that ac impedance spectroscopy is carried out using electrochemical workstation, test result are shown in Fig. 2, wherein a is to make in embodiment 1 in Fig. 2
The ionic conductivity test result of standby PFSA-Na solid union electrolyte membrance, b is to prepare in comparative example 1 in Fig. 2
The ionic conductivity test result of pure PFSA-Na solid electrolyte diaphragm, as shown in Figure 2, a and b is it is found that PFSA- in comparison diagram 2
Impedance value of the impedance value of Na solid union electrolyte membrance significantly less than pure PFSA-Na solid electrolyte diaphragm, therefore PFSA-
The conductivity at room temperature of Na solid union electrolyte membrance is apparently higher than pure PFSA-Na solid electrolyte diaphragm.This is because
During preparing PFSA-Na solid union electrolyte membrance, electrolyte joined, solute is electrolysed composite solid in electrolyte
Free sodium ion quantity in matter diaphragm increases, meanwhile, the solvent in electrolyte has plasticization to solid electrolyte membrane, can
The crystallinity of macromolecule matrix is reduced, so that the molecule segment more disorder of its part, vibration, migration is more violent, so make
The PFSA-Na solid union electrolyte membrance finally prepared has excellent conductivity at room temperature.
(2) ionic conductivity for the PFSA-Na solid union electrolyte membrance that testing example 2 is prepared into embodiment 3
The PFSA-Na solid union electrolyte membrance that embodiment 2 is prepared into embodiment 3 is clipped in two stainless steels respectively
Between electrode, it is assembled into CR2032 type battery respectively, carries out the test of ac impedance spectroscopy using electrochemical workstation at room temperature,
Test result is successively shown in Fig. 3, Fig. 4 and Fig. 5, and curve and abscissa intersection point may be considered the overall electrical resistance of film in each figure
(totalresistance), i.e. R, by Fig. 3 to Fig. 5 it is found that the PFSA-Na solid union that embodiment 2 is prepared into embodiment 3
The overall electrical resistance of electrolyte membrance is all very low, according to formula δ=L/ (R*S) it is found that embodiment 2 was prepared into embodiment 3
PFSA-Na solid union electrolyte membrance all has ideal conductivity at room temperature.
Embodiment 6
Application of the PFSA-Na solid union electrolyte membrance prepared in embodiment 1 in secondary solid-state sodium-ion battery
(1) NVP@C, tetra- kinds of NFP@C, NMVP@C and HQ-NaFe positive electrodes are prepared
The sodium acetate of stoichiometric ratio, ammonium metavanadate will be met, ammonium dihydrogen phosphate is ground in the agate mortar with suitable amount of sucrose
10min is ground, 10mL ethyl alcohol is then added, continues to be ground to until ethyl alcohol volatilizees completely, powdered presoma can be obtained, by this
Powdered presoma is placed in tube furnace, in argon atmosphere, is warming up to 700 DEG C with 5 DEG C/min heating rate, isothermal holding 6
Hour to get arrive NVP@C.
The sodium acetate of stoichiometric ratio, ferric oxalate, sucrose and ammonium dihydrogen phosphate and ethanol in proper amount mixing and ball milling will be met
For 24 hours, ball milling products therefrom is then dried into 3h at 60 DEG C, obtains precursor powder, by the precursor powder in argon atmosphere
In with the heating rate of 3 DEG C/min, isothermal holding 12h is in 600 DEG C to get NFP@C.
The sodium acetate of stoichiometric ratio will be met, manganese acetate and vanadium acetylacetonate ground and mixed in the agate mortar
10min obtains mixed-powder, and the phosphoric acid (14.63M) for meeting stoichiometric ratio is added into the mixed-powder and 10mL is anhydrous
Ethyl alcohol continues ground and mixed, and until ethyl alcohol volatilizees obtain powder precursor completely, which is placed in tube furnace
In, 650 DEG C are warming up to the heating rate of 5 DEG C/min under protection of argon gas, and isothermal holding 8h is to get arriving NMVP@C.
968mg ten is weighed first and is hydrated sodium ferrocyanide, is dissolved in 100mL deionized water and is obtained clear solution, in machinery
Under stirring, 1mL hydrochloric acid (37%) is added into the clear solution, 4h is persistently stirred at 60 DEG C, then after being filtered, being washed, In
It is dried in vacuo at 100 DEG C for 24 hours to get HQ-NaFe.
(2) by tetra- kinds of NVP@C obtained in step (1), NFP@C, NMVP@C and HQ-NaFe positive electrodes respectively with acetylene
After black and Kynoar is mixed according to mass ratio 70:20:10, a small amount of N-Methyl pyrrolidone is added, in agate mortar
It is ground to homogeneous black paste, then is equably coated in black paste anode sizing agent is obtained on the aluminium foil that diameter is 13mm, is passed through
120 DEG C of vacuum drying 12h are to get four kinds of positive plates.
(3) the PFSA-Na solid union that will be prepared in the positive plate containing NVP@C prepared in step (2), embodiment 1
Electrolyte membrance and sodium metal move in the glove box full of argon gas the assembling for carrying out solid-state sodium-ion battery (button cell),
The button cell model used is CR2032, then enterprising in Land test macro by battery removal glove box after assembling
Row electrochemical property test, test voltage range are 1.5-4.0V, and test results are shown in figure 6, wherein a is the battery in Fig. 6
B is the cycle performance of battery figure in the charging and discharging curve figure of cyclic process, Fig. 6, by a in Fig. 6 it is found that NVP@C and PFSA-Na
When solid union electrolyte membrance is assembled into solid-state sodium-ion battery, there is apparent charge and discharge platform, this and its in common electricity
The electrochemical behavior shown in solution liquid is consistent.A can also be seen that the specific discharge capacity of the battery first circle reaches from Fig. 6
106mAhg-1, it has excellent performance, and the charging and discharging curve registration of 50,100 and 200 circles is higher, polarizes small, illustrates the electricity
Pond invertibity in cyclic process is good.Have good circulation steady it is found that the battery is during actual cycle by b in Fig. 6
Qualitative, cycle life is small up to reversible capacity decaying in 200 circles, cyclic process, and coulombic efficiency approaches always in cyclic process
100%, illustrate that the related electrochemical reaction in its cyclic process has the invertibity of height, further demonstrates by implementing
The PFSA-Na solid union electrolyte membrance and NVP@C-material prepared in example 1 has good matching in stored energy application
Energy.
(4) the PFSA-Na solid union that will be prepared in the positive plate containing NFP@C prepared in step (2), embodiment 1
Electrolyte membrance and sodium metal move in the glove box full of argon gas the assembling for carrying out solid-state sodium-ion battery (button cell),
The button cell model used is CR2032, then enterprising in Land test macro by battery removal glove box after assembling
Row electrochemical property test, test voltage range are 1.5-4.0V, and test results are shown in figure 7, wherein a is the battery in Fig. 7
B is the cycle performance of battery figure in the charging and discharging curve figure of cyclic process, Fig. 7, by a in Fig. 7 it is found that NFP@C and PFSA-Na
When solid union electrolyte membrance is assembled into solid-state sodium-ion battery, there is apparent charge and discharge platform, this is with the material general
The electrochemical behavior shown in logical electrolyte is consistent.A can also be seen that the charge and discharge specific volume of the battery first circle from Fig. 7
Amount has reached 126 and 84mAhg-1, it has excellent performance, and the charging and discharging curve registration of 50,100 and 200 circles is higher, explanation
Battery invertibity in cyclic process is good.By b in Fig. 7 it is found that the battery has good follow during actual cycle
Ring stability, cycle life is up to 200 circles, and reversible capacity decaying is small in cyclic process, and coulombic efficiency is always in cyclic process
Close to 100%, illustrate that related electrochemical reaction in its cyclic process has the invertibity of height, further demonstrate by
The PFSA-Na solid union electrolyte membrance and NFP@C-material prepared in embodiment 1 has good matching in stored energy application
Performance.
(5) the PFSA-Na solid union that will be prepared in the positive plate containing NMVP@C prepared in step (2), embodiment 1
Electrolyte membrance and sodium metal move in the glove box full of argon gas the assembling for carrying out solid-state sodium-ion battery (button cell),
The button cell model used is CR2032, then enterprising in Land test macro by battery removal glove box after assembling
Row electrochemical property test, test voltage range are 2.5-3.8V, and test results are shown in figure 8, wherein a is the battery in Fig. 8
B is the cycle performance of battery figure in the charging and discharging curve figure of cyclic process, Fig. 8, by a in Fig. 8 it is found that NMVP@C and PFSA-
When Na solid union electrolyte membrance is assembled into solid-state sodium-ion battery, there is apparent charge and discharge platform, this exists with the material
The electrochemical behavior shown in general electrolytic liquid is consistent.A can also be seen that the charge and discharge ratio of the battery first circle from Fig. 8
Capacity has reached 101 and 87mAhg-1, it has excellent performance, and the charging and discharging curve registration of 50,100 and 193 circles is higher, pole
Change small, illustrates that battery invertibity in cyclic process is good.By b in Fig. 8 it is found that the battery has during actual cycle
Good cyclical stability, cycle life is small up to reversible capacity decaying in 200 circles, cyclic process, and coulomb in cyclic process
Efficiency illustrates that the related electrochemical reaction in its cyclic process has the invertibity of height, further always close to 100%
Demonstrate the PFSA-Na solid union electrolyte membrance by preparing in embodiment 1 has in stored energy application with NMVP@C-material
Good matching performance.
(6) the PFSA-Na solid-state prepared in the positive plate containing HQ-NaFe prepared in step (2), embodiment 1 is multiple
It closes electrolyte membrance and sodium metal moves in the glove box full of argon gas the group for carrying out solid-state sodium-ion battery (button cell)
Dress, the button cell model used is CR2032, after assembling, by battery removal glove box, then in Land test macro
Upper carry out electrochemical property test, test voltage range are 2-4.2V, and test results are shown in figure 9, wherein a is the electricity in Fig. 9
Pond is in the charging and discharging curve figure of cyclic process, and b is the cycle performance of battery figure in Fig. 9, by a in Fig. 9 it is found that HQ-NaFe with
When PFSA-Na solid union electrolyte membrance is assembled into solid-state sodium-ion battery, there is apparent charge and discharge platform, this and the material
Expect that the electrochemical behavior shown in general electrolytic liquid is consistent.A can also be seen that the charge and discharge of the battery first circle from Fig. 9
Electric specific capacity has reached 51 and 122mAhg-1, have excellent performance, and 50,100 and 200 circle charging and discharging curve registrations compared with
Height polarizes small, illustrates that battery invertibity in cyclic process is good.By b in Fig. 9 it is found that the battery is in actual cycle process
In there is good cyclical stability, cycle life is up to 200 circles, and reversible capacity decaying is small in cyclic process, and cyclic process
Middle coulombic efficiency illustrates that the related electrochemical reaction in its cyclic process has the invertibity of height always close to 100%,
The PFSA-Na solid union electrolyte membrance by preparing in embodiment 1 is further demonstrated with HQ-NaFe material in stored energy application
In have good matching performance.
Above 4 kinds of positive electrodes can be assembled into solid-state sodium-ion battery (knob with PFSA-Na solid union electrolyte membrance
Detain battery), and it has excellent performance, preparation method is simple, raw material is easy to get, it was demonstrated that the present invention has huge commercial promise.
Embodiment 7
Sodium-ion battery based on the assembling of PFSA-Na solid union electrolyte membrance at low temperature test by operational capability
The PFSA-Na prepared in the positive plate containing HQ-NaFe prepared in 3 step of embodiment (2), embodiment 1 is solid
State composite electrolyte diaphragm and sodium metal move to progress solid-state sodium-ion battery (button cell) in the glove box full of argon gas
Assembling, the button cell model used be CR2032, after assembling, by battery removal glove box, then Land test
Carry out electrochemical property test in system, test voltage range is 2-4.2V, and in test process, battery and battery folders are placed
In high-low temperature chamber, to carry out temperature control.Wherein, during low temperature test, used low temperature is respectively 5 DEG C, -5 DEG C with
And -15 DEG C, before different cryogenic temperature tests starts, battery is stood to 1h at such a temperature in advance to reach temperature
Balance, each cryogenic temperature test loop circle number are 60 circles, and low-temperature circulating charge/discharge capacity and coulombic efficiency are as shown in Figure 10,
As shown in Figure 10, the battery recycle at low temperature still keep stablize, capacity attenuation is small, coulombic efficiency still be maintained at~
100%, thus illustrating the sodium-ion battery assembled based on PFSA-Na solid union electrolyte membrance at low temperature is still had in fact
Border operational capability.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with
Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of the technical program, should all be covered in the present invention
Scope of the claims in.
Claims (10)
1. a kind of preparation method of PFSA-Na solid union electrolyte membrance, which is characterized in that the method is as follows:
PFSA-Li powder is added to the water mixing together with sodium source, 5-24h is stirred at 40-150 DEG C, then through centrifuge washing,
Drying obtains PFSA-Na powder, obtains PFSA-Na glue, In after the PFSA-Na powder is then dissolved in organic solvent
Electrolyte is added under stirring into the PFSA-Na glue, mixed solution is obtained, after finally being scratched the mixed solution
Dry 12-48h, is made PFSA-Na solid union electrolyte membrance at 60-150 DEG C.
2. the method as described in claim 1, which is characterized in that the PFSA-Li powder and the mass ratio of sodium source are 1-100:
1-400。
3. the method as described in claim 1, which is characterized in that the mass fraction of PFSA-Na powder in the PFSA-Na glue
For 20-40%；The volume ratio of the PFSA-Na glue and electrolyte is 0.5-200:1；The concentration of the electrolyte is 1mol/
L。
4. the method according to claim 1, which is characterized in that the sodium source is sodium chloride, sodium acetate, nitric acid
One of sodium, sodium hydroxide or sodium carbonate.
5. the method according to claim 1, which is characterized in that the centrifuge washing is specially in 5000-
With deionized water centrifuge washing 3-10 times under the speed of 9000r/min, each centrifuge washing 3-5min.
6. the method according to claim 1, which is characterized in that the drying is specially to dry at 30-150 DEG C
5-96h。
7. the method according to claim 1, which is characterized in that the organic solvent is nitrogen nitrogen dimethyl formyl
One of amine, N-Methyl pyrrolidone, acetonitrile, tetrahydrofuran or dimethyl sulfoxide.
8. the method according to claim 1, which is characterized in that solute is sodium perchlorate, six in the electrolyte
One of sodium fluoro phosphate, trifluoromethanesulfonic acid sodium or bis trifluoromethyl sulfimide sodium, in the electrolyte solvent be EC/DEC,
One of EC/PC, DGM or DME.
9. the PFSA-Na solid union electrolyte membrance of the described in any item method preparations of claim 1-8.
10. application of the PFSA-Na solid union electrolyte membrance as claimed in claim 9 in secondary solid-state sodium-ion battery.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111341980A (en) * | 2020-02-24 | 2020-06-26 | 河北科技大学 | Sodium perfluorosulfonate ion battery electrolyte membrane and preparation method and application thereof |
| CN112563564A (en) * | 2020-11-13 | 2021-03-26 | 上海空间电源研究所 | Soft chemical synthesis method for preparing sodium ion solid electrolyte |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1277740A (en) * | 1998-09-01 | 2000-12-20 | 索尼株式会社 | Method for producing nonaqueous gel electrolyte cell |
| CN108539259A (en) * | 2017-03-03 | 2018-09-14 | 北京纳米能源与系统研究所 | Perfluor sodium polymer electrolyte and its preparation method and application and all-solid sodium ion battery and friction nanometer power generator system |
-
2019
- 2019-08-09 CN CN201910736151.6A patent/CN110416627B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1277740A (en) * | 1998-09-01 | 2000-12-20 | 索尼株式会社 | Method for producing nonaqueous gel electrolyte cell |
| CN108539259A (en) * | 2017-03-03 | 2018-09-14 | 北京纳米能源与系统研究所 | Perfluor sodium polymer electrolyte and its preparation method and application and all-solid sodium ion battery and friction nanometer power generator system |
Non-Patent Citations (1)
| Title |
|---|
| JIN, ZHAOQING 等: ""Application of lithiated Nafion ionomer film as", 《JOURNAL OF POWER SOURCES》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111341980A (en) * | 2020-02-24 | 2020-06-26 | 河北科技大学 | Sodium perfluorosulfonate ion battery electrolyte membrane and preparation method and application thereof |
| CN112563564A (en) * | 2020-11-13 | 2021-03-26 | 上海空间电源研究所 | Soft chemical synthesis method for preparing sodium ion solid electrolyte |
| CN112563564B (en) * | 2020-11-13 | 2021-11-09 | 上海空间电源研究所 | Soft chemical synthesis method for preparing sodium ion solid electrolyte |
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