CN106129350A - A kind of solid-state sode cell and preparation method thereof - Google Patents
A kind of solid-state sode cell and preparation method thereof Download PDFInfo
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- CN106129350A CN106129350A CN201610509855.6A CN201610509855A CN106129350A CN 106129350 A CN106129350 A CN 106129350A CN 201610509855 A CN201610509855 A CN 201610509855A CN 106129350 A CN106129350 A CN 106129350A
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
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Abstract
The invention discloses a kind of solid-state sode cell and preparation method thereof.This solid-state sode cell includes positive pole, negative pole and solid electrolyte.Wherein, positive pole or positive pole and negative pole use the material of sodium ion conduction to carry out thin layer modification.And give the preparation method of solid-state sode cell, when metal is as negative pole, use the material of sodium ion conduction to carry out thin layer modification at the positive pole of solid-state sode cell；When nonmetal as negative pole time, the material that positive pole and the negative pole at solid-state sode cell all uses sodium ion to conduct electricity carries out thin layer modification.Solid-state sode cell prepared by the method using the present invention to provide, owing to electrode has been carried out thin layer modification, greatly reduce the internal resistance of solid-state sode cell, cycle performance and high rate performance are excellent, security performance is good, and there is practical value, may be used for solar electrical energy generation, wind-power electricity generation, intelligent grid peak regulation, distribution power station, back-up source or the extensive energy storage device of communication base station.
Description
Technical field
The present invention relates to field of material technology, particularly relate to a kind of solid-state sode cell and preparation method thereof.
Background technology
Lithium rechargeable battery has that specific energy density is big, operating temperature range width, discharge and recharge life-span length, self discharge are little,
The advantages such as memory-less effect is little, its mass energy density can reach 280Wh/kg it is considered to be the most promising electrochmical power source.Closely
All show, at electrokinetic cell and energy-storage battery field, the development prospect attracted people's attention over Nian.
But, tellurian lithium resource does not enrich, and elemental lithium abundance in the earth's crust is only 0.0065%, and is distributed
The most uneven, along with following electric automobile, the arrival in intelligent grid epoch, the price that lithium resource is short and expensive necessarily becomes
Restrict the key factor of its development.Accordingly, it would be desirable to the energy-storage battery system of Development of Novel.And the abundance that sodium is in the earth's crust reaches
2.64%, cheap, and sodium ion has similar embedding mechanism, sodium ion secondary battery weight the most in recent years with lithium ion
Newly paid close attention to by people.
On the other hand, the most traditional secondary cell many employings liquid organic electrolyte, leakage, electrode corrosion easily occur
Etc. problem, at an excessive temperature, in some instances it may even be possible to blast.Although using polymer dielectric can alleviate these to a certain extent
Problem, but can not fundamentally solve.And use inorganic solid electrolyte, it is possible not only to get rid of the leakage that brings of electrolyte and asks
, and there is not the resolution problem of liquid electrolyte in topic so that solid-state sode cell security performance higher (Nature, 2008,451
(7179): 652-657, Nature, 2001,414 (6861): 359-367), cycle life longer (J.Power Sources,
2005,147(1-2):269-281).Additionally, development solid-state sode cell, also help the miniaturization of battery, shape of product many
Sample (Adv.Energy Mater., 2011,1 (1): 10-33).Solid electrolyte also acts the effect of barrier film simultaneously, therefore
Simplify the structure of battery, it is not necessary under protective atmosphere, carry out the encapsulation of battery, reduce cost of manufacture.
Development solid-state sode cell, it is crucial that find the high solid electrolyte of ionic conductivity and reduce electrode material and
The great interface resistance that solid-solid contact between solid electrolyte is brought.Wherein the contact problems between solid-solid are from very great Cheng
The performance of solid-state sode cell is determined on degree.Can be by the method for ball milling or at active material surface coating electrolyte thin film
The contact area increased in combination electrode between electrode active material and electrolyte powder passes to the ion improving combination electrode
Lead performance, or reduce the interface resistance between electrode and solid electrolyte by the method for high-temperature heat treatment, thus promote
The performance of solid-state sode cell.
But above-mentioned treating method technique is the most complicated, and cost is high, it would be desirable to seek that a kind of preparation technology is simple, low cost
Honest and clean, formation efficiency is high, and be applicable to industrialization produce solution.
Summary of the invention
It is an object of the invention to provide the contact between electrode and solid electrolyte in a kind of concrete reduction solid-state sode cell
The method of resistance, i.e. uses the material of sodium ion conduction to carry out thin layer modification in electrode material surface, and provides containing thin layer
The preparation method of the solid-state sode cell of decorative material.
First aspect, the invention provides a kind of solid-state sode cell, including positive pole, negative pole and solid electrolyte, at one
In embodiment, described positive pole uses sodium ion conductive material to carry out thin layer modification.
Preferably, described sodium ion conductive material is electrolyte, fuse salt or ionic liquid.
It is further preferred that described electrolyte is NaClO4/EC-DEC、NaClO4/PC、NaClO4/EC-DMC、NaClO4/
EC-DEC-PC、NaClO4/EC-DMC-PC、NaPF6/PC、NaPF6/EC-DEC、NaFSI/EC-DMC-PC、NaPF6/EC-DEC-
PC、NaPF6/EC-DMC-PC、NaFSI/EC-DEC、NaPF6/ EC-DMC, NaFSI/EC-DMC, NaFSI/EC-DEC-PC or
NaFSI/PC；Described fuse salt is NaFSI-KFSI, NaFSI-LiFSI or NaFSI-KFSI-LiFSI；Described ionic liquid is
N-methyl-N-propylpiperidinium-bis(fluorosulfonyl)imide(PP13FSI)、N-methyl-N-
propylpyrrolidinium-bis(trifluoromethanesulfonyl)imide(PYR13TFSI)、N-
methoxyethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)-im ide
(PYR1,2O1TFSI)、N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide
(PYR14FSI)、N-butyl-N-ethylpyrrolidinium bis(fluorosulfonyl)imide(PYR24FSI)、N-
butyl-N-ethylpyrrolidinium bis(trifluorosulfonyl)imide(PYR24TFSI)、1-butyl-1-
methylpyrrolidinium bis(trifluoromethanesulfonyl)imide(C4mpyr-TFSI)、NaTFSI-
PYR24TFSI、NaTFSI-PYR13TFSI、NaTFSI-PYR1,2O1TFSI、NaFSI-PYR14FSI、NaFSI-PYR24FSI or
NaFSI-PP13FSI。
Second aspect, the invention provides the preparation method of a kind of solid-state sode cell as described in relation to the first aspect, including: will
Positive active material mixes with certain proportion with electrolyte powder, conductive carbon black, binding agent, grinds or stirs, being coated to
Potsherd surface；Dry between room temperature to 120 DEG C, be transferred in glove box；Metal negative electrode is attached to the another side of potsherd,
Drip thin layer decorative material in positive pole side, be packaged.
Preferably, the quality of described sodium ion conductive material accounts for the 1-50% of positive pole gross mass.
The third aspect, the invention provides the preparation method of a kind of solid-state sode cell as described in relation to the first aspect, including: will
Positive active material mixes with certain proportion with thin layer decorative material, adds a certain proportion of electrolyte powder, conductive carbon black,
Grind or stir, being coated to potsherd surface；Dry between room temperature to 120 DEG C, be transferred in glove box；Metal is born
Pole is attached to the another side of potsherd, is packaged.
Preferably, the quality of described sodium ion conductive material accounts for the 1-50% of positive pole gross mass.
Fourth aspect, the invention provides a kind of solid-state sode cell, including positive pole, negative pole and solid electrolyte, at one
In embodiment, described positive pole and described negative pole all use sodium ion conductive material to carry out thin layer modification.
Preferably, described sodium ion conductive material is electrolyte, fuse salt or ionic liquid.
It is further preferred that described electrolyte is NaClO4/EC-DEC、NaClO4/PC、NaClO4/EC-DMC、NaClO4/
EC-DEC-PC、NaClO4/EC-DMC-PC、NaPF6/PC、NaPF6/EC-DEC、NaFSI/EC-DMC-PC、NaPF6/EC-DEC-
PC、NaPF6/EC-DMC-PC、NaFSI/EC-DEC、NaPF6/ EC-DMC, NaFSI/EC-DMC, NaFSI/EC-DEC-PC or
NaFSI/PC；Described fuse salt is NaFSI-KFSI, NaFSI-LiFSI or NaFSI-KFSI-LiFSI；Described ionic liquid is
N-methyl-N-propylpiperidinium-bis(fluorosulfonyl)imide(PP13FSI)、N-methyl-N-
propylpyrrolidinium-bis(trifluoromethanesulfonyl)imide(PYR13TFSI)、N-
methoxyethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)-im ide
(PYR1,2O1TFSI)、N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide
(PYR14FSI)、N-butyl-N-ethylpyrrolidinium bis(fluorosulfonyl)imide(PYR24FSI)、N-
butyl-N-ethylpyrrolidinium bis(trifluorosulfonyl)imide(PYR24TFSI)、1-butyl-1-
methylpyrrolidinium bis(trifluoromethanesulfonyl)imide(C4mpyr-TFSI)、NaTFSI-
PYR24TFSI、NaTFSI-PYR13TFSI、NaTFSI-PYR1,2O1TFSI、NaFSI-PYR14FSI、NaFSI-PYR24FSI or
NaFSI-PP13FSI。
5th aspect, the invention provides the preparation method of a kind of solid-state sode cell as described in fourth aspect, including: will
Positive active material mixes with certain proportion with electrolyte powder, conductive carbon black, binding agent, grinds or stirs, being coated to
Potsherd surface, dries between room temperature to 120 DEG C；Again by negative electrode active material and electrolyte powder, conductive carbon black, binding agent
Mix with certain proportion, grind or stir, being coated to the another side of potsherd, dry between room temperature to 120 DEG C, just
Negative pole both sides drip thin layer decorative material respectively, are packaged.
Preferably, the quality of the sodium ion conductive material in described positive pole accounts for the 1-50% of positive pole gross mass；Described negative pole
In the quality of sodium ion conductive material account for the 1-50% of negative pole gross mass.
6th aspect, the invention provides the preparation method of a kind of solid-state sode cell as described in fourth aspect, including: will
Positive active material mixes with certain proportion with thin layer decorative material, adds a certain proportion of electrolyte powder, conductive carbon black,
Grind or stir, being coated to potsherd surface, drying between room temperature to 120 DEG C；Again by negative electrode active material with thin
Layer decorative material mixes with certain proportion, adds a certain proportion of electrolyte powder, conductive carbon black, grinds or stir, and is coated with
It is layed onto the another side of potsherd, dries between room temperature to 120 DEG C, be packaged.
Preferably, the quality of the sodium ion conductive material in described positive pole accounts for the 1-50% of positive pole gross mass；Described negative pole
In the quality of sodium ion conductive material account for the 1-50% of negative pole gross mass.
Electrode material surface is coated with by the employing thin layer decorative material that the present invention provides, and assembles solid-state sode cell
Preparation technology is simple, with low cost, formation efficiency is high, it is adaptable to industrialization generates.Solid-state prepared by the method for the application present invention
Sode cell, cycle performance and high rate performance are excellent, and security performance is good, has great practical value, may be used for solar electrical energy generation,
Wind-power electricity generation, intelligent grid peak regulation, distribution power station, back-up source or the extensive energy storage device of communication base station.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
In having technology to describe, the required accompanying drawing used is introduced briefly.It should be evident that reflect in accompanying drawings below is only this
A part of embodiment of invention, for those of ordinary skill in the art, on the premise of not paying creative work, also
Other embodiments of the present invention can be obtained according to these accompanying drawings.And all these embodiment or embodiment are all the present invention's
Within protection domain.
Fig. 1 is the solid-state sode cell charging and discharging curve figure of the embodiment of the present invention 7 preparation；
Fig. 2 is the solid-state sode cell high rate performance figure of the embodiment of the present invention 7 preparation；
Fig. 3 is the solid-state sode cell impedance spectrogram of the embodiment of the present invention 7 preparation；
Fig. 4 is the solid-state sode cell charging and discharging curve figure of the embodiment of the present invention 8 preparation；
Fig. 5 is the solid-state sode cell impedance spectrogram of the embodiment of the present invention 8 preparation；
Fig. 6 is the solid-state sode cell charging and discharging curve figure of the embodiment of the present invention 9 preparation；
Fig. 7 is the solid-state sode cell impedance spectrogram of the embodiment of the present invention 9 preparation；
Fig. 8 is the solid-state sode cell charging and discharging curve figure of the embodiment of the present invention 10 preparation；
Fig. 9 is the solid-state sode cell impedance spectrogram of the embodiment of the present invention 10 preparation；
Figure 10 is the solid-state full battery charging and discharging curve chart of the embodiment of the present invention 11 preparation；
Figure 11 is the solid-state sode cell charging and discharging curve figure of the embodiment of the present invention 12 preparation；
Figure 12 is the solid-state sode cell charging and discharging curve figure of the embodiment of the present invention 13 preparation；
Figure 13 is the solid-state sode cell charging and discharging curve figure of the embodiment of the present invention 14 preparation；
Figure 14 is the solid-state sode cell charging and discharging curve figure of the embodiment of the present invention 15 preparation；
Figure 15 is the solid-state sode cell charging and discharging curve figure of comparative example 1 of the present invention preparation；
Figure 16 is the solid-state sode cell impedance spectrogram of comparative example 1 of the present invention preparation；
Figure 17 is the solid-state sode cell anode structure schematic diagram of comparative example 1 of the present invention preparation；
Figure 18 is solid-state sode cell anode structure schematic diagram prepared by the embodiment of the present invention.
Detailed description of the invention
Below by accompanying drawing and specific embodiment, the present invention is further detailed, it should be appreciated that these
Embodiment is only used for being described in more detail and is used, and should not be construed as with limiting the present invention in any form, is i.e. not intended to
Limit the scope of the invention.
This part to the present invention test used in material and test method carry out general description.Although it is
Realize many materials that the object of the invention used and operational approach is to it is known in the art that but the present invention still uses up at this
May describe in detail.It will be apparent to those skilled in the art that within a context, if not specified, material therefor of the present invention and behaviour
It is well known in the art as method.
Embodiment 1
The embodiment of the present invention 1 provides a kind of solid-state sode cell, and this solid-state sode cell includes positive pole, negative pole and solid state electrolysis
Matter, wherein, positive pole uses sodium ion conductive material to carry out thin layer modification.It is to say, this solid-state sode cell except include positive pole,
Negative pole and solid electrolyte, also include sodium ion conductive material, and the thin layer decorative material as positive pole uses in the battery.Preferably
Ground, the thin layer decorative material used in solid-state sode cell is electrolyte, fuse salt or ionic liquid.Wherein,
Preferably, electrolyte is NaClO4/EC-DEC、NaClO4/PC、NaClO4/EC-DMC、NaClO4/EC-DEC-PC、
NaClO4/EC-DMC-PC、NaPF6/PC、NaPF6/EC-DEC、NaFSI/EC-DMC-PC、NaPF6/EC-DEC-PC、NaPF6/
EC-DMC-PC、NaFSI/EC-DEC、NaPF6/ EC-DMC, NaFSI/EC-DMC, NaFSI/EC-DEC-PC or NaFSI/PC etc.；
Preferably, fuse salt is NaFSI-KFSI, NaFSI-LiFSI or NaFSI-KFSI-LiFSI etc.；
Preferably, ionic liquid is: N-methyl-N-propylpiperidinium-bis (fluorosulfonyl) im
ide(PP13FSI)、N-methyl-N-propylpyrrolidinium-bis(trifluoromethanesulfonyl)im
ide(PYR13TFSI)、N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethanesul
fonyl)-imide(PYR1,2O1TFSI)、N-butyl-N-methylpyrrolidinium bis(trifluoromethane
sulfonyl)imide(PYR14FSI)、N-butyl-N-ethylpyrrolidinium bis(fluorosulfonyl)imide
(PYR24FSI)、N-butyl-N-ethylpyrrolidinium bis(trifluorosulfonyl)imide(PYR24TF
SI)、1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide(C4mpyr-
TFSI)、NaTFSI-PYR24TFSI、NaTFSI-PYR13TFSI、NaTFSI-PYR1,2O1TFSI、NaFSI-PYR14FSI、NaFSI-
PYR24FSI or NaFSI-PP13FSI etc..
It should be noted that in solid-state sodium-ion battery, thin layer decorative material, in addition to being coated on positive electrode surface, also may be used
To be positioned in the hole of the positive pole of solid state battery, or between positive pole and solid electrolyte.Now, utilize metal as solid-state sodium
The negative pole of battery, thin layer decorative material is added on positive pole side, and thin layer decorative material can mix during preparing electrode
Add, it is also possible to after prepared by electrode, add during assemble.
The solid-state sode cell that the present embodiment provides, positive pole have employed sodium ion conductive material and carries out thin layer modification, greatly
Reduce the interface resistance between electrode and solid electrolyte, there is cycle performance and high rate performance is excellent, security performance is good
Advantage, has great practical value, may be used for solar electrical energy generation, wind-power electricity generation, intelligent grid peak regulation, distribution power station, standby
Power supply or the extensive energy storage device of communication base station.
Embodiment 2
The embodiment of the present invention 2 provides a kind of solid-state sode cell, and this solid-state sode cell includes positive pole, negative pole and solid state electrolysis
Matter, wherein, positive pole and negative pole all use sodium ion conductive material to carry out thin layer modification.It is to say, this solid-state sode cell except
Including positive pole, negative pole and solid electrolyte, also including sodium ion conductive material, the thin layer as positive pole and negative pole is repaiied in the battery
Exterior material uses.Preferably, the thin layer decorative material used in solid-state sode cell is electrolyte, fuse salt or ionic liquid.
Wherein,
Preferably, electrolyte is NaClO4/EC-DEC、NaClO4/PC、NaClO4/EC-DMC、NaClO4/EC-DEC-PC、
NaClO4/EC-DMC-PC、NaPF6/PC、NaPF6/EC-DEC、NaFSI/EC-DMC-PC、NaPF6/EC-DEC-PC、NaPF6/
EC-DMC-PC、NaFSI/EC-DEC、NaPF6/ EC-DMC, NaFSI/EC-DMC, NaFSI/EC-DEC-PC or NaFSI/PC；
Preferably, fuse salt is NaFSI-KFSI, NaFSI-LiFSI or NaFSI-KFSI-LiFSI；
Preferably, ionic liquid is: N-methyl-N-propylpiperidinium-bis (fluorosulfonyl)
imide(PP13FSI)、N-methyl-N-propylpyrrolidinium-bis(trifluoromethanesulfonyl)
imide(PYR13TFSI)、N-methoxyethyl-N-methylpyrrolidinium bis
(trifluoromethanesulfonyl)-imide(PYR1,2O1TFSI)、N-butyl-N-methylpyrrolidinium
bis(trifluoromethanesulfonyl)imide(PYR14FSI)、N-butyl-N-ethylpyrrolidinium bis
(fluorosulfonyl)imide(PYR24FSI)、N-butyl-N-ethylpyrrolidinium bis
(trifluorosulfonyl)imide(PYR24TFSI)、1-butyl-1-methylpyrrolidinium bis
(trifluoromethanesulfonyl)imide(C4mpyr-TFSI)、NaFSI-PP13FSI、NaTFSI-PYR13TFSI、
NaTFSI-PYR1,2O1TFSI、NaFSI-PYR14FSI、NaFSI-PYR24FSI or NaTFSI-PYR24TFSI。
It should be noted that in solid-state sodium-ion battery, thin layer decorative material is except being coated on the table of positive pole and negative pole
Outside face, it is also possible to be positioned in the positive pole of solid state battery and the hole of negative pole, or between positive pole and solid electrolyte and negative pole with
Between solid electrolyte.Now, the nonmetal negative pole as solid-state sode cell, the both positive and negative polarity both sides of solid-state sode cell are utilized
Add thin layer decorative material.Thin layer decorative material can be mixed into during preparing electrode, it is also possible to has prepared at both positive and negative polarity
After, add during assemble.
The solid-state sode cell that the present embodiment provides, positive pole and negative pole all have employed sodium ion conductive material to carry out thin layer and repaiies
Decorations, greatly reduce the interface resistance between electrode and solid electrolyte, have cycle performance and high rate performance is excellent, safety
The advantages such as performance is good, have great practical value, may be used for solar electrical energy generation, wind-power electricity generation, intelligent grid peak regulation, distribution electricity
Stand, back-up source or the extensive energy storage device of communication base station.
Embodiment 3
Present embodiments providing the preparation method of solid-state sode cell in embodiment 1, metal Na is as solid-state sode cell
Negative pole, carries out thin layer modification to positive pole, carries out during assemble, and its preparation process is:
Positive active material is mixed with certain proportion with electrolyte powder, conductive carbon black, binding agent, grinds or stir all
Even, it is coated to potsherd surface；Dry between room temperature to 120 DEG C, be transferred in glove box；Metal Na is attached to potsherd
Another side, drips thin layer decorative material, is packaged in positive pole side.Preferably, in preparation process, thin layer decorative material
Quality is the 1-50% of positive pole gross mass.
The preparation method of solid-state sode cell that the present embodiment provides is simple, raw material is easy to get and with low cost, be suitable for
In the extensive application manufactured.The solid-state sode cell using the present embodiment preparation method to obtain has cycle performance and high rate performance
The advantages such as excellence, security performance are good, have great practical value, may be used for solar electrical energy generation, wind-power electricity generation, intelligent grid tune
Peak, distribution power station, back-up source or the extensive energy storage device of communication base station.
Embodiment 4
Present embodiments providing the preparation method of solid-state sode cell in embodiment 1, metal Na is as solid-state sode cell
Negative pole, carries out thin layer modification to positive pole, carries out during preparing electrode, and its preparation process is:
Positive active material is mixed with certain proportion with thin layer decorative material, add a certain proportion of electrolyte powder,
Conductive carbon black, grinds or stirs, and is coated to potsherd surface；Dry between room temperature to 120 DEG C, be transferred to glove box
In；Metal Na is attached to the another side of potsherd, is packaged.Preferably, in preparation process, the quality of thin layer decorative material
1-50% for positive pole gross mass.
Embodiment 5
Present embodiments provide the preparation method of solid-state sode cell in embodiment 2, nonmetal as solid-state sode cell
Negative pole, all carries out thin layer modification to positive pole and negative pole, carries out when assemble, and its preparation process is:
Positive active material is mixed with certain proportion with electrolyte powder, conductive carbon black, binding agent, grinds or stir all
Even, it is coated to potsherd surface；Dry between room temperature to 120 DEG C；By positive active material and electrolyte powder, conductive carbon
Black, binding agent mixes with certain proportion, grinds or stirs, being coated to potsherd surface, dries between room temperature to 120 DEG C
Dry；Drip thin layer decorative material respectively in both positive and negative polarity both sides, be packaged.Preferably, in preparation process, positive pole adds
The quality of thin layer decorative material is the 1-50% of positive pole gross mass, and it is total that the quality of the thin layer decorative material added in negative pole accounts for negative pole
The 1-50% of quality.
Embodiment 6
Present embodiments provide the preparation method of solid-state sode cell in embodiment 2, nonmetal as solid-state sode cell
Negative pole, all carries out thin layer modification to positive pole and negative pole, carries out during preparing electrode, and its preparation process is:
Positive active material is mixed with certain proportion with thin layer decorative material, add a certain proportion of electrolyte powder,
Conductive carbon black, grinds or stirs, and is coated to potsherd surface；Dry between room temperature to 120 DEG C, be transferred to glove box
In；Again negative electrode active material is mixed with certain proportion with thin layer decorative material, add a certain proportion of electrolyte powder, conduction
Carbon black, grinds or stirs, and is coated to potsherd surface；Dry between room temperature to 120 DEG C, be transferred in glove box；Enter
Row encapsulation.
Preferably, in preparation process, the 1-that quality is positive pole gross mass of the thin layer decorative material added in positive pole
50%, the quality of the thin layer decorative material added in negative pole accounts for the 1-50% of negative pole gross mass.
The preparation method of solid-state sode cell that the present embodiment provides is simple, raw material is easy to get and with low cost, be suitable for
In the extensive application manufactured.The solid-state sode cell using the present embodiment preparation method to obtain has cycle performance and high rate performance
The advantages such as excellence, security performance are good, have great practical value, may be used for solar electrical energy generation, wind-power electricity generation, intelligent grid tune
Peak, distribution power station, back-up source or the extensive energy storage device of communication base station.
The technical scheme provided for a better understanding of the present invention, following is described separately the application present invention with multiple instantiations
The preparation method that above-described embodiment 3-6 provides carries out detailed process prepared by solid-state sode cell, then measures prepared solid-state
Sode cell characteristic, and carry out chemical property contrast with the solid-state sode cell being not added with thin layer decorative material.
Embodiment 7
The present embodiment 7 use the preparation method in embodiment 3 positive pole of solid-state sode cell is carried out thin layer modify improve
The cyclicity of battery and the most forthright.
Ionic liquid is used as the thin layer decorative material of solid-state sode cell.Concretely comprise the following steps:
Weigh 20mg Na respectively3.3Zr1.7La0.3Si2PO12Electrolyte powder, 10mg conductive carbon black, 60mg positive electrode active material
Matter Na3V2(PO4)3, and measure the PVDF binding agent mix homogeneously that 200 μ L concentration are 50mg/mL, add 100 μ L N-methyl pyrroles
Pyrrolidone (NMP) diluent, grinds to form slurry in the environment of normal temperature drying, then slurry is coated uniformly on solid electrolyte
On potsherd, it is transferred in 50 DEG C of baking ovens be dried, makes NMP volatilize completely, obtain being coated with the potsherd of positive pole.
Being assemblied in glove box of battery is carried out.One side uncoated for potsherd after above-mentioned heat treatment is sticked metal Na
Sheet, and 5 μ L PP13FSI ionic liquids are dripped in positive pole side, it is assembled into battery and seals.
The battery being assembled at room temperature is tested, and test voltage scope is 2.5～3.7V, and charging and discharging curve is shown in Fig. 1.
Fig. 1 demonstrates the 1st week and the charging and discharging curve of the 10th week.It can be seen that first all charge specific capacity are up to 115.6mAh/g, first week
Coulombic efficiency be 97.2%, after circulating 10 weeks, reversible specific capacity is still maintained at 114mAh/g.Fig. 2 gives the most forthright
Can, the reversible specific capacity under 0.2C, 0.5C, 1C, 2C, 4C, 6C, 8C and 10C multiplying power is respectively 113mAh/g, 112mAh/g,
109mAh/g, 106mAh/g, 103mAh/g, 97mAh/g, 91mAh/g and 86mAh/g, when multiplying power returns to 0.2C, capacity can be complete
Entirely return to 113mAh/g.Fig. 3 is the battery impedance spectrogram when room temperature, the wherein electricity of first semicircle correspondence solid electrolyte
Resistance, second semicircle represents interface resistance.It can be seen that after positive pole side adds ionic liquid, interface impedance value is the most several
Ten ohm.
Embodiment 8
The present embodiment 8 use the preparation method in embodiment 4 positive pole of solid-state sode cell is carried out thin layer modify improve
The cyclicity of battery and the most forthright.
Fuse salt is used for the thin layer decorative material of solid-state sode cell.Concretely comprise the following steps:
Weigh 20mg Na respectively3.15Zr1.85Al0.15Si2PO12Electrolyte powder and 10mg mol ratio are the NaFSI-of 1:1
KFSI mix homogeneously, and add 60mg positive active material NaTi2(PO4)3, 10mg conductive carbon black, in the environment of normal temperature drying
Grind to form slurry, then slurry is coated uniformly on solid electrolyte ceramic sheet, be transferred in 50 DEG C of baking ovens be dried, be coated with
It is covered with the potsherd of positive pole.
Being assemblied in glove box of battery is carried out.
The battery being assembled into is tested at 80 DEG C, and test voltage scope is 1.5～2.8V, and charging and discharging curve is shown in Fig. 4.
Illustrating the discharge and recharge behavior of first week in Fig. 4, first Zhou Fang electricity and charge specific capacity are respectively 119.1mAh/g and 116.9mAh/
g.Fig. 5 is the battery impedance spectrogram when 80 DEG C, now only has a semicircle on impedance spectrogram, represents interface resistance.Can see
Going out, after adding fuse salt between positive pole and electrolyte, when 80 DEG C, interface impedance value is only tens ohm.
Embodiment 9
The present embodiment 9 use the preparation method in embodiment 3 positive pole of solid-state sode cell is carried out thin layer modify improve
The cyclicity of battery and the most forthright.
Electrolyte is used for the thin layer decorative material of solid-state sode cell.Concretely comprise the following steps:
Weigh 30mg Na respectively3.25Zr1.75Y0.25Si2PO12Solid electrolyte powder, 50mg positive active material Na3V2
(PO4)3, 10mg conductive carbon black, and measure the PVDF binding agent mix homogeneously that 200 μ L concentration are 50mg/mL, add appropriate N-
Methyl pyrrolidone (NMP) solution, grinds to form slurry in the environment of normal temperature drying, then slurry is coated uniformly on solid electricity
Solve on matter potsherd, be transferred in 80 DEG C of baking ovens be dried, obtain being coated with the potsherd of positive pole.
Being assemblied in glove box of battery is carried out.One side uncoated for above-mentioned potsherd is sticked metal Na sheet, in coating
5 μ L NaPF are added in the side having positive pole6/ EC-DMC electrolyte, is assembled into battery and seals.
The battery being assembled at room temperature is tested, and test voltage scope is 2.5～3.7V, and charging and discharging curve is shown in Fig. 6.
Fig. 6 illustrates the 1st week and the discharge and recharge behavior of the 10th week, first week charging and discharging specific capacity be respectively 117.3mAh/g and
114.4mAh/g, the reversible specific capacity of the 10th week is maintained at 115.6mAh/g.Fig. 7 is the battery impedance spectrogram when room temperature, its
In the resistance of first semicircle correspondence solid electrolyte, second semicircle represents interface resistance.It can be seen that add in positive pole side
After entering electrolyte, interface impedance value is only tens ohm.
Embodiment 10
The present embodiment 10 use the preparation method in embodiment 3 positive pole of solid-state sode cell is carried out thin layer modify improve
The cyclicity of battery and the most forthright.
Electrolyte is used for the thin layer decorative material of solid-state sode cell.Concretely comprise the following steps:
Weigh 20mg Na respectively3Zr2Ge0.2Si1.8PO12Solid electrolyte powder, 50mg positive active material Na3
(VOPO4)2F, 10mg conductive carbon black, and measure the PVDF mix homogeneously that 200 μ L concentration are 50mg/mL, add appropriate N-methyl
Ketopyrrolidine (NMP) solution, grinds to form slurry in the environment of normal temperature drying, then slurry is coated uniformly on solid electrolyte
On potsherd, it is transferred in 70 DEG C of baking ovens be dried, obtains being coated with the potsherd of positive pole.
Being assemblied in glove box of battery is carried out.One side uncoated for above-mentioned potsherd is sticked metal Na sheet, in coating
10 μ L NaClO are added in the side having positive pole4/ EC-DMC electrolyte, is assembled into battery and seals.
The battery being assembled at room temperature is tested, and test voltage scope is 3.0～4.2V, and charging and discharging curve is shown in Fig. 8.
Illustrating the discharge and recharge behavior of the 1st week in Fig. 8, first all charging and discharging specific capacities are respectively 126.9mAh/g and 114.6mAh/
g.Fig. 9 is the battery impedance spectrogram when room temperature, the wherein resistance of first semicircle correspondence solid electrolyte, second semicircle generation
Surface and interface resistance.It can be seen that after positive pole side adds electrolyte, interface impedance value is only tens ohm.
Embodiment 11
The present embodiment 11 uses the preparation method in embodiment 5 that positive pole and the negative pole of solid-state sode cell are carried out thin layer modification
Improve the cyclicity of battery and the most forthright.
Ionic liquid is used for the thin layer decorative material of solid-state sode cell.Concretely comprise the following steps:
Weigh 20mg Na respectively3.15Zr1.85Al0.15Si2PO12Solid electrolyte powder, 60mg positive active material Na3V2
(PO4)3, 10mg white carbon black, and measure the PVDF binding agent mix homogeneously that 200 μ L concentration are 50mg/mL, add the N-methyl of 50 μ L
Ketopyrrolidine (NMP), grinds to form slurry in the environment of normal temperature drying, then slurry is coated uniformly on solid electrolyte ceramic
On sheet, it is transferred in 50 DEG C of baking ovens be dried.Weigh 20mg Na respectively3.15Zr1.85Al0.15Si2PO12Solid electrolyte powder,
60mg negative electrode active material NaTi2(PO4)3, 10mg conductive carbon black, and measure the PVDF binding agent that 200 μ L concentration are 50mg/mL
Mix homogeneously, adds the N-Methyl pyrrolidone (NMP) of 50 μ L, grinds to form slurry, then slurry in the environment of normal temperature drying
Material is coated uniformly on the another side of solid electrolyte ceramic sheet, is transferred in 50 DEG C of baking ovens be dried.
Being assemblied in glove box of battery is carried out.The above-mentioned potsherd both sides being coated with both positive and negative polarity are dripped respectively 10 μ L from
Sub-liquid, is assembled into battery and seals.
The battery being assembled at room temperature is tested, and test voltage scope is 0～2.0V, and charging and discharging curve is shown in Figure 10.
Illustrating the discharge and recharge behavior of the 1st week in Figure 10, first all reversible specific capacities are 103mAh/g.
Embodiment 12
The present embodiment 12 use the preparation method in embodiment 6 positive pole of solid-state sode cell is carried out thin layer modify improve
The cyclicity of battery and the most forthright.
Ionic liquid is used for the thin layer decorative material of solid-state sode cell.Concretely comprise the following steps:
Weigh 50mg positive active material Na respectively0.66Ni0.33Mn0.67O2Mix with 30mg PYR13TFSI ionic liquid
Uniformly, then weigh 10mg Na-β "-Al2O3Solid electrolyte powder, 10mg conductive black, grind in the environment of normal temperature drying
Form slurry, is then coated uniformly on Na-β "-Al slurry2O3On solid electrolyte ceramic sheet, it is transferred in 50 DEG C of baking ovens be dried.
Being assemblied in glove box of battery is carried out.One side uncoated for above-mentioned potsherd is sticked metal Na sheet, is assembled into
Battery also seals.
The battery being assembled into is tested at 25 DEG C, and test voltage scope is 2.5～3.8V, and charging and discharging curve is shown in figure
11.Illustrating the discharge and recharge behavior of the 1st week in Figure 11, first all charging capacitys are 69mAh/g, and specific discharge capacity is 72mAh/g.
Embodiment 13
The present embodiment 13 use the preparation method in embodiment 6 positive pole of solid-state sode cell is carried out thin layer modify improve
The cyclicity of battery and the most forthright.
Ionic liquid is used for the thin layer decorative material of solid-state sode cell.Concretely comprise the following steps:
Weigh 60mg positive active material Na respectively0.66Ni0.33Mn0.67O2Mix with 20mg PYR13TFSI ionic liquid
Uniformly, then weigh 10mg Na-β "-Al2O3Solid electrolyte powder, 10mg conductive black, grind in the environment of normal temperature drying
Form slurry, is then coated uniformly on Na-β "-Al slurry2O3On solid electrolyte ceramic sheet, it is transferred in 50 DEG C of baking ovens be dried.
Being assemblied in glove box of battery is carried out.One side uncoated for above-mentioned potsherd is sticked metal Na sheet, is assembled into
Battery also seals.
The battery being assembled into is tested at 70 DEG C, and test voltage scope is 2.5～3.8V, and charging and discharging curve is shown in figure
12.Illustrating the discharge and recharge behavior of the 1st week in Figure 12, first all charging capacitys are 69mAh/g, and specific discharge capacity is 80mAh/g.
Embodiment 14
The present embodiment 14 use the preparation method in embodiment 4 positive pole of solid-state sode cell is carried out thin layer modify improve
The cyclicity of battery and the most forthright.
Ionic liquid is used for the thin layer decorative material of solid-state sode cell.Concretely comprise the following steps:
Weigh 60mg positive active material Na respectively0.9Ni0.4Mn0.4Ti0.2O2Mix with 20mg PYR13TFSI ionic liquid
Close uniformly, then weigh 10mg Na-β "-Al2O3Solid electrolyte powder, 10mg conductive black, be added in the environment of normal temperature drying
Under grind to form slurry, then slurry is coated uniformly on Na-β "-Al2O3On solid electrolyte ceramic sheet, it is transferred to 50 DEG C of baking ovens
In be dried.
Being assemblied in glove box of battery is carried out.One side uncoated for above-mentioned potsherd is sticked metal Na sheet, is assembled into
Battery also seals.
The battery being assembled into is tested at 80 DEG C, and test voltage scope is 2.5～4.1V, and charging and discharging curve is shown in figure
13.Illustrating the discharge and recharge behavior of the 1st week in Figure 13, second week charging capacity is 109mAh/g, and specific discharge capacity is 104mAh/
g。
Embodiment 15
The present embodiment 15 use the preparation method in embodiment 4 positive pole of solid-state sode cell is carried out thin layer modify improve
The cyclicity of battery and the most forthright.
Ionic liquid is used for the thin layer decorative material of solid-state sode cell.Concretely comprise the following steps:
Weigh 50mg positive active material Na respectively3V2(PO4)3With 20mg PP13FSI ionic liquid mix homogeneously, then claim
Take 25mg Na3.3Zr1.7La0.3Si2PO12Solid electrolyte powder, 5mg conductive black, grind to form in the environment of normal temperature drying
Slurry, is then coated uniformly on Na slurry3.3Zr1.7La0.3Si2PO12On solid electrolyte ceramic sheet, it is transferred to 50 DEG C of baking ovens
In be dried.
Being assemblied in glove box of battery is carried out.One side uncoated for above-mentioned potsherd is sticked metal Na sheet, is assembled into
Battery also seals.
The battery being assembled into is tested at 80 DEG C, and test voltage scope is 2.5～3.8V, and charging and discharging curve is shown in figure
14.Illustrating the discharge and recharge behavior of the 1st week in Figure 14, within the 1st week, charging capacity is 115mAh/g, and specific discharge capacity is
107.2mAh/g。
Comparative example 1
This comparative example 1 is prepared for a kind of conventional solid-state sode cell, does not add thin layer between positive pole and solid electrolyte
Decorative material, and at room temperature measure its chemical property.
Concretely comprise the following steps: 20mg Na will be weighed respectively3.3Zr1.7La0.3Si2PO12Solid electrolyte powder, 60mg positive pole are lived
Property material Na3V2(PO4)3, 10mg conductive carbon black, and measure the PVDF binding agent mix homogeneously that 200 μ L concentration are 50mg/mL, add
Enter 100 μ L N-Methyl pyrrolidone (NMP) diluent, in the environment of normal temperature drying, grind to form slurry, then that slurry is uniform
It is coated on solid electrolyte ceramic sheet, is transferred in baking oven be dried, obtains being coated with the potsherd of positive pole.
Being assemblied in glove box of battery is carried out.One side uncoated for above-mentioned potsherd is sticked metal Na sheet, is assembled into
Battery also seals.
The battery being assembled at room temperature is tested, and test voltage scope is 2.5～3.7V, and charging and discharging curve is shown in figure
15.Illustrating the 1st week and the discharge and recharge behavior of the 2nd week in Figure 15, first all charging capacitys are only 48.5mAh/g, specific discharge capacity
For 44mAh/g, within the 2nd week, charge specific capacity is 38.8mAh/g, and specific discharge capacity is 37.7mAh/g.Not only reversible specific capacity is far away
It is less than the battery having added interface thin layer decorative material, and polarization is also greatly increased (～200mV).Figure 16 is that battery is when room temperature
Impedance spectrogram, the wherein resistance of first semicircle correspondence solid electrolyte, second semicircle represents interface resistance.It can be seen that
Interface impedance value is up to tens kilohms.Figure 17 is solid-state sode cell anode structure schematic diagram prepared by comparative example, can by Figure 17
To find out, for conventional solid-state sode cell positive pole, its active material and solid electrolyte are point cantact, and contact area is little, interface
Resistance is big；Figure 18 is solid-state sode cell anode structure schematic diagram prepared by the embodiment of the present invention, as seen from Figure 18, the present invention
Solid-state sode cell positive pole prepared by embodiment, its sodium ion can be entered by the sodium ion conductive material decorative layer of surface of active material
Row conduction, it is possible to achieve contacting with the face of solid electrolyte, interface resistance is little.
By above-described embodiment, by adding ionic liquid, fuse salt or electrolysis in the electrode of solid-state sode cell
Liquid, as thin layer decorative material, can increase the contact area of electrode and solid electrolyte, add ion can pathway, aobvious
Work reduces interface resistance, and the chemical property of battery can be significantly improved.Use the preparation method that the present invention provides
The solid-state sode cell obtained has the advantages such as cycle performance and high rate performance are excellent, security performance is good, has great practical value,
May be used for the extensive of solar electrical energy generation, wind-power electricity generation, intelligent grid peak regulation, distribution power station, back-up source or communication base station
Energy storage device.
Although present invention has been a certain degree of description, it will be apparent that, without departing from the spirit and scope of the present invention
Under the conditions of, the suitable change of each condition can be carried out.It is appreciated that and the invention is not restricted to described embodiment, and be attributed to right
The scope required, it includes the equivalent of described each factor.
Above-described detailed description of the invention, has been carried out the purpose of the present invention, technical scheme and beneficial effect further
Describe in detail, be it should be understood that the detailed description of the invention that the foregoing is only the present invention, be not intended to limit the present invention
Protection domain, all within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. done, all should comprise
Within protection scope of the present invention.
Claims (14)
1. a solid-state sode cell, including positive pole, negative pole and solid electrolyte, it is characterised in that described positive pole uses sodium ion
Conductive material carries out thin layer modification.
Solid-state sode cell the most according to claim 1, it is characterised in that described sodium ion conductive material is electrolyte, melts
Melt salt or ionic liquid.
Solid-state sode cell the most according to claim 1, it is characterised in that described electrolyte is NaClO4/EC-DEC、
NaClO4/PC、NaClO4/EC-DMC、NaClO4/EC-DEC-PC、NaClO4/EC-DMC-PC、NaPF6/PC、NaPF6/EC-
DEC、NaFSI/EC-DMC-PC、NaPF6/EC-DEC-PC、NaPF6/EC-DMC-PC、NaFSI/EC-DEC、NaPF6/EC-DMC、
NaFSI/EC-DMC, NaFSI/EC-DEC-PC or NaFSI/PC；Described fuse salt be NaFSI-KFSI, NaFSI-LiFSI or
NaFSI-KFSI-LiFSI；Described ionic liquid is N-methyl-N-propylpiper idinium-bis
(fluorosulfonyl)imide(PP13FSI)、N-methyl-N-propylpyrrolidinium-bis
(trifluoromethanesulfonyl)imide(PYR13TFSI)、N-methoxyethyl-N-methylpyrrolid
inium bis(trifluoromethanesulfonyl)-imide(PYR1,2O1TFSI)、N-butyl-N-methylpyrro
lidinium bis(trifluoromethanesulfonyl)imide(PYR14FSI)、N-butyl-N-ethylpyrrolidi
nium bis(fluorosulfonyl)imide(PYR24FSI)、N-butyl-N-ethylpyrrolidinium bis(trifl
uorosulfonyl)imide(PYR24TFSI)、1-butyl-1-methylpyrrolidinium bis(trifluorometh
anesulfonyl)imide(C4mpyr-TFSI)、NaTFSI-PYR24TFSI、NaTFSI-PYR13TFSI、NaTFSI-PYR1, 2O1TFSI、NaFSI-PYR14FSI、NaFSI-PYR24FSI or NaFSI-PP13FSI。
4. the preparation method of the solid-state sode cell as described in any one of claim 1-3, it is characterised in that described method bag
Include:
Positive active material is mixed with certain proportion with electrolyte powder, conductive carbon black, binding agent, grinds or stir,
It is coated to potsherd surface；Dry between room temperature to 120 DEG C, be transferred in glove box；Metal negative electrode is attached to potsherd
Another side, drips thin layer decorative material, is packaged in positive pole side.
Preparation method the most according to claim 4, it is characterised in that it is total that the quality of described sodium ion conductive material accounts for positive pole
The 1-50% of quality.
6. the preparation method of the solid-state sode cell as described in any one of claim 1-3, it is characterised in that described method bag
Include:
Positive active material is mixed with certain proportion with thin layer decorative material, adds a certain proportion of electrolyte powder, lead
Electrical carbon is black, grinds or stirs, and is coated to potsherd surface；Dry between room temperature to 120 DEG C, be transferred in glove box；
Metal negative electrode is attached to the another side of potsherd, is packaged.
Preparation method the most according to claim 6, it is characterised in that it is total that the quality of described sodium ion conductive material accounts for positive pole
The 1-50% of quality.
8. a solid-state sode cell, including positive pole, negative pole and solid electrolyte, it is characterised in that described positive pole and described negative pole
Sodium ion conductive material is all used to carry out thin layer modification.
Solid-state sode cell the most according to claim 8, it is characterised in that described sodium ion conductive material is electrolyte, melts
Melt salt or ionic liquid.
Solid-state sode cell the most according to claim 8, it is characterised in that described electrolyte is NaClO4/EC-DEC、
NaClO4/PC、NaClO4/EC-DMC、NaClO4/EC-DEC-PC、NaClO4/EC-DMC-PC、NaPF6/PC、NaPF6/EC-
DEC、NaFSI/EC-DMC-PC、NaPF6/EC-DEC-PC、NaPF6/EC-DMC-PC、NaFSI/EC-DEC、NaPF6/EC-DMC、
NaFSI/EC-DMC, NaFSI/EC-DEC-PC or NaFSI/PC；Described fuse salt be NaFSI-KFSI, NaFSI-LiFSI or
NaFSI-KFSI-LiFSI；Described ionic liquid is N-methyl-N-propylpiper idinium-bis
(fluorosulfonyl)imide(PP13FSI)、N-methyl-N-propylpyrrolidinium-bis
(trifluoromethanesulfonyl)imide(PYR13TFSI)、N-methoxyethyl-N-methylpyrrolid
inium bis(trifluoromethanesulfonyl)-imide(PYR1,2O1TFSI)、N-butyl-N-methylpyrro
lidinium bis(trifluoromethanesulfonyl)imide(PYR14FSI)、N-butyl-N-ethylpyrrolidi
nium bis(fluorosulfonyl)imide(PYR24FSI)、N-butyl-N-ethylpyrrolidinium bis(trifl
uorosulfonyl)imide(PYR24TFSI)、1-butyl-1-methylpyrrolidinium bis(trifluorometh
anesulfonyl)imide(C4mpyr-TFSI)、NaTFSI-PYR24TFSI、NaTFSI-PYR13TFSI、NaTFSI-PYR1, 2O1TFSI、NaFSI-PYR14FSI、NaFSI-PYR24FSI or NaFSI-PP13FSI。
The preparation method of 11. 1 kinds of solid-state sode cells as described in any one of claim 8-10, it is characterised in that described method
Including:
Positive active material is mixed with certain proportion with electrolyte powder, conductive carbon black, binding agent, grinds or stir,
It is coated to potsherd surface, dries between room temperature to 120 DEG C；Again by negative electrode active material and electrolyte powder, conductive carbon black,
Binding agent mixes with certain proportion, grinds or stirs, being coated to the another side of potsherd, dries between room temperature to 120 DEG C
Dry, drip thin layer decorative material respectively in both positive and negative polarity both sides, be packaged.
12. preparation methoies according to claim 11, it is characterised in that the matter of the sodium ion conductive material in described positive pole
Amount accounts for the 1-50% of positive pole gross mass；The quality of the sodium ion conductive material in described negative pole accounts for the 1-50% of negative pole gross mass.
The preparation method of 13. 1 kinds of solid-state sode cells as described in any one of claim 8-10, it is characterised in that described method
Including:
Positive active material is mixed with certain proportion with thin layer decorative material, adds a certain proportion of electrolyte powder, lead
Electrical carbon is black, grinds or stirs, and is coated to potsherd surface, dries between room temperature to 120 DEG C；Again by negative electrode active material
Mix with certain proportion with thin layer decorative material, add a certain proportion of electrolyte powder, conductive carbon black, grind or stir all
Even, it is coated to the another side of potsherd, dries between room temperature to 120 DEG C, be packaged.
14. preparation methoies according to claim 13, it is characterised in that the matter of the sodium ion conductive material in described positive pole
Amount accounts for the 1-50% of positive pole gross mass；The quality of the sodium ion conductive material in described negative pole accounts for the 1-50% of negative pole gross mass.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106711465A (en) * | 2017-01-20 | 2017-05-24 | 江南山 | Composite negative-pole tube for battery |
| CN107331848A (en) * | 2017-07-12 | 2017-11-07 | 中国科学院宁波材料技术与工程研究所 | A kind of composite positive pole of all solid state sodium rechargeable battery and a kind of all solid state sodium rechargeable battery |
| CN108695552A (en) * | 2018-07-11 | 2018-10-23 | 中国科学院宁波材料技术与工程研究所 | NASICON structures sodion solid electrolytes, preparation method and solid-state sodium-ion battery |
| CN108933282A (en) * | 2018-07-11 | 2018-12-04 | 中国科学院宁波材料技术与工程研究所 | NASICON structure sodion solid electrolytes, preparation method and solid-state sodium-ion battery |
| CN109860700A (en) * | 2019-01-16 | 2019-06-07 | 广东工业大学 | A kind of Nasicon structure sodion solid electrolytes and its preparation method and application |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100273062A1 (en) * | 2009-04-28 | 2010-10-28 | Toyota Jidosha Kabushiki Kaisha | All-solid-state battery |
| CN103579605A (en) * | 2012-08-01 | 2014-02-12 | 中国科学院物理研究所 | Sodium ion secondary battery, active substance, positive electrode and negative electrode used by sodium ion secondary battery, and preparation method of active substance |
| CN105374980A (en) * | 2014-08-15 | 2016-03-02 | 中国科学院物理研究所 | An interface infiltrated quasi-solid alkali metal cell, electrodes of the cell and a preparing method of the cell |
-
2016
- 2016-06-30 CN CN201610509855.6A patent/CN106129350A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100273062A1 (en) * | 2009-04-28 | 2010-10-28 | Toyota Jidosha Kabushiki Kaisha | All-solid-state battery |
| CN103579605A (en) * | 2012-08-01 | 2014-02-12 | 中国科学院物理研究所 | Sodium ion secondary battery, active substance, positive electrode and negative electrode used by sodium ion secondary battery, and preparation method of active substance |
| CN105374980A (en) * | 2014-08-15 | 2016-03-02 | 中国科学院物理研究所 | An interface infiltrated quasi-solid alkali metal cell, electrodes of the cell and a preparing method of the cell |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106711465A (en) * | 2017-01-20 | 2017-05-24 | 江南山 | Composite negative-pole tube for battery |
| CN106711465B (en) * | 2017-01-20 | 2023-07-21 | 江南山 | Composite negative electrode tube for battery |
| CN107331848A (en) * | 2017-07-12 | 2017-11-07 | 中国科学院宁波材料技术与工程研究所 | A kind of composite positive pole of all solid state sodium rechargeable battery and a kind of all solid state sodium rechargeable battery |
| CN107331848B (en) * | 2017-07-12 | 2020-03-17 | 中国科学院宁波材料技术与工程研究所 | Composite positive electrode material of all-solid-state sodium secondary battery and all-solid-state sodium secondary battery |
| CN109872883A (en) * | 2017-12-01 | 2019-06-11 | 中国科学院大连化学物理研究所 | A kind of supercapacitor electrolyte and the supercapacitor comprising it |
| CN108695552A (en) * | 2018-07-11 | 2018-10-23 | 中国科学院宁波材料技术与工程研究所 | NASICON structures sodion solid electrolytes, preparation method and solid-state sodium-ion battery |
| CN108933282A (en) * | 2018-07-11 | 2018-12-04 | 中国科学院宁波材料技术与工程研究所 | NASICON structure sodion solid electrolytes, preparation method and solid-state sodium-ion battery |
| CN108933282B (en) * | 2018-07-11 | 2021-01-22 | 中国科学院宁波材料技术与工程研究所 | NASICON structure sodium ion solid electrolyte, preparation method thereof and solid sodium ion battery |
| CN109860700A (en) * | 2019-01-16 | 2019-06-07 | 广东工业大学 | A kind of Nasicon structure sodion solid electrolytes and its preparation method and application |
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