CN110311167A - A kind of composite solid electrolyte piece and preparation method thereof and solid state battery - Google Patents
A kind of composite solid electrolyte piece and preparation method thereof and solid state battery Download PDFInfo
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- CN110311167A CN110311167A CN201910748639.0A CN201910748639A CN110311167A CN 110311167 A CN110311167 A CN 110311167A CN 201910748639 A CN201910748639 A CN 201910748639A CN 110311167 A CN110311167 A CN 110311167A
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
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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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention provides a kind of composite solid electrolyte pieces, comprising: the poly-dopamine layer on the electrolyte sheet surface is arranged in electrolyte sheet.Poly-dopamine layer in composite solid electrolyte piece provided by the invention is evenly distributed, can deformation occurs, solid electrolyte surface and positive electrode surface in solid state battery can be made to realize good interface contact, the influence that the volume change that electrode material occurs in cyclic process contacts electrode/electrolyte interface can be effectively reduced, reduce interface impedance, to promote the cycle performance and service life of battery.The present invention also provides the preparation methods and solid state battery of a kind of composite solid electrolyte piece.
Description
Technical field
The present invention relates to battery technology field more particularly to a kind of composite solid electrolyte piece and preparation method thereof and solid-states
Battery.
Background technique
In order to alleviate the status of current environment deterioration, changes existing unreasonable energy resource structure, energy is cleaned to novel green
The exploitation and storage in source become urgent task.For the utilization for realizing green clean energy resource, to, technology small by territory restriction at
The research of ripe electrochemical energy storage technology is most important.Therefore, exploitation is efficiently, safety, capacity is big, service life is long, and can be
Stablize the secondary cell to release energy when use to be of great significance.
Since a series of advantages, the lithium ion batteries such as energy density height, long service life are widely used in 3C Product,
And there is applications well prospect in terms of power battery and smart grid energy storage.However, the electrolysis that lithium ion battery uses at present
Liquid easily occurs to burn and explode, and affects the large-scale application of lithium ion battery, therefore improves its safety issue as weight
Point research direction.Using the all-solid-state battery very good solution safety problem of battery of safe and stable solid electrolyte, together
When also effectively increase battery energy density, therefore be the important directions of following battery development.
However, belonging to point-to-point connect due to contacting in a manner of solid/liquid/solid interface between solid electrolyte and electrode material
Touching, contact area hinder carrier in the transmission at interface much smaller than the contact between electrolyte and electrode material, therefore complete solid
State battery still has the excessive problem of interface resistance.In addition, volume change can occur for electrode material during charge and discharge cycles
Change, the contact area between solid electrolyte and electrode material is caused to further decrease.Above-mentioned factor will lead to all-solid-state battery
In charge and discharge cycles capacity gradually decrease, high rate performance it is poor, directly affect the energy density and power density of battery.Cause
This, the above problem for how solving solid state battery becomes the hot spot of this field research.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of composite solid electrolytes and preparation method thereof and solid-state electricity
The solid state battery in pond, composite electrolyte preparation provided by the invention has preferable cycle performance.
The present invention provides a kind of composite solid electrolyte pieces, comprising:
Electrolyte sheet；
The poly-dopamine layer of the electrolyte layer surface is set.
In the present invention, the material of the electrolyte sheet can solid electrolyte, Garnet knot selected from NASICON structure
One of solid electrolyte and the solid electrolyte of perovskite structure of structure.
In the present invention, the thickness of the electrolyte sheet can be 0.1~1mm, or 0.2~0.8mm, it can be with
For 0.3~0.6mm.
In the present invention, the ingredient of the poly-dopamine layer is mainly poly-dopamine.In the present invention, the poly-dopamine
The thickness of layer can be 2~500nm, or 10~400nm, or 50~300nm, or 100~
250nm can also be 150~200nm.
In the present invention, a side surface of electrolyte sheet is arranged in the poly-dopamine layer.
The present invention provides a kind of preparation methods of composite solid electrolyte piece described in above-mentioned technical proposal, comprising:
Dopamine hydrochloride, auxiliary agent and solvent are mixed, dopamine polymeric solution is obtained；
It is dry after the dopamine polymeric solution and electrolyte sheet are mixed, obtain composite solid electrolyte piece.
In the present invention, the auxiliary agent can selected from trishydroxymethylaminomethane, cetyl trimethylammonium bromide or
Polyvinyl alcohol.
In the present invention, the solvent can be selected from water, ethyl alcohol or isopropanol.
In the present invention, the mass ratio of the Dopamine hydrochloride, auxiliary agent and solvent can be (1~30): (0.05~1):
100, can also be (5~25): (0.1~0.8): 100, or (10~20): (0.3~0.7): 100.
In the present invention, the mixed method can be with are as follows:
Auxiliary agent and solvent are mixed, mixed liquor is obtained；
Dopamine hydrochloride is added in mixed liquor, dopamine polymeric solution is obtained.
In the present invention, the dopamine polymeric solution and the method for electrolyte sheet mixing can be with are as follows:
By electrolyte sheet infiltration in dopamine polymeric solution.
It in the present invention, can be with before the electrolyte sheet and dopamine polymeric solution being mixed further include:
Electrolyte sheet surface is polished and cleaned.
In the present invention, the reagent of the cleaning can be ethyl alcohol.
In the present invention, the electrolyte sheet and the temperature of dopamine polymeric solution mixing can be 40~80 DEG C, can also
Think 50~70 DEG C, can also be 60 DEG C；The time of the electrolyte sheet and the mixing of dopamine polymeric solution can be 10~15
Hour, or 12~13 hours；To complete the growth of electrolyte sheet surface poly-dopamine layer.
It in the present invention, can be with before the drying further include:
It will be rinsed with water with the mixed electrolyte sheet of dopamine polymeric solution.
In the present invention, the water can be distilled water.
In the present invention, the drying can carry out in an oven.In the present invention, the temperature of the drying can be 70
~90 DEG C, or 75~85 DEG C, can also be 80 DEG C；The time of the drying can be 10~15 hours, or
12~13 hours.
The present invention provides a kind of solid state batteries, comprising: negative electrode material, composite solid electrolyte piece and anode composite material
Material.
In the present invention, the material of the negative electrode material can be selected from lithium metal, metallic sodium or alloy；The alloy can be with
Selected from lithium indium alloy or lithium-tin alloy.
In the present invention, the shape of the negative electrode material can be sheet；The thickness of sheet-like cathode material can for 0.1~
3mm, or 0.5~2.5mm can also be 1~2mm.
In the present invention, the composite solid electrolyte piece and composite solid electrolyte piece one described in above-mentioned technical proposal
It causes, details are not described herein.
In the present invention, the anode composite may include:
Positive electrode, solid electrolyte powder, conductive additive and binder.
In the present invention, the positive electrode can be selected from FeS2、Fe1-xS、WS2、Na3V2(PO4)3、LiCoO2、
LiFePO4, NCM or NCA.
In the present invention, the material of the solid electrolyte powder can selected from NASICON structure solid electrolyte,
One or more of solid electrolyte and the solid electrolyte of perovskite structure of Garnet structure.
In the present invention, the granularity of the solid electrolyte powder can be 0.1~10 μm, or 0.5~8 μm, also
It can be 2~6 μm.
In the present invention, the conductive additive can be selected from Ketjen black, acetylene black, Super P, carbon nanotube and stone
One or more of black alkene.
In the present invention, the binder can be selected from ethyl cellulose (EC), Kynoar (PVDF), sodium alginate
(SA) and one or more of sodium carboxymethylcellulose (CMC).
In the present invention, the mass ratio of the positive electrode, solid electrolyte powder, conductive additive and binder can be
(45~70): (15~40): (10~20): (5~15), or (50~65): (20~35): (12~18): (8~
12), can also be (55~60): (25~30): (14~16): 15.
In the present invention, the shape of the anode composite can be stratiform, and the thickness of lamellar composite positive electrode can be
0.1~500 μm, or 0.5~400 μm, or 1~300 μm, or 10~200 μm, or 50~
150 μm, can also be 100 μm.
In the present invention, the preparation method of the anode composite can be with are as follows:
Positive electrode, solid electrolyte powder, conductive additive, binder and solvent are mixed, anode sizing agent is obtained；
The anode sizing agent is coated in composite solid electrolyte piece with drying behind the surface of poly-dopamine layer side, is obtained
To anode composite.
In the present invention, the type and dosage of the positive electrode, solid electrolyte powder, conductive additive and binder with
Positive electrode described in above-mentioned technical proposal, solid electrolyte powder, conductive additive and the type of binder are consistent with dosage, herein
It repeats no more.
In the present invention, the solvent can be selected from one or both of N-Methyl pyrrolidone and terpinol.This hair
The bright dosage to the solvent does not have special limitation, and the solvent can dissolve the ingredient in above-mentioned positive electrode.
In the present invention, the consistency of thickness of the thickness of the coating and the layered anode composite of above-mentioned technical proposal,
This is repeated no more.
In the present invention, the temperature of the drying can be 70~90 DEG C, or 75~85 DEG C, can also be 80
℃；The time of the drying can be 10~15 hours, or 12~13 hours.
In the present invention, the solid state battery may include:
Composite solid electrolyte piece；
The anode composite that the composite solid electrolyte piece has poly-dopamine layer layer of surface is set；
The negative electrode material of another side surface of composite solid electrolyte piece is set.
In the present invention, the preparation method of the solid state battery can be with are as follows:
Anode composite is supported on the surface that composite solid electrolyte piece has poly-dopamine layer side；
In the other side area load negative electrode material of the composite solid electrolyte piece, it is assembled into battery and seals, obtain
Solid state battery.
In the present invention, described that anode composite is supported on composite solid electrolyte piece with one side surface of poly-dopamine layer
Method it is consistent with the preparation method of anode composite described in above-mentioned technical proposal, details are not described herein.
In the present invention, the load negative electrode material can carry out under an inert atmosphere, more can be in inert atmosphere gloves
It is carried out in case.
The present invention optimizes the interface of solid electrolyte and electrode material, by being arranged one on solid electrolyte surface
Layer is evenly distributed, it is abundant contact, can the high molecular polymer poly-dopamine decorative layer that deformation occurs, to reach improvement solid electrolytic
The purpose of matter and electrode material contacts.Studies have shown that the addition of poly-dopamine decorative layer can obviously improve solid-state electricity in the present invention
The cycle performance in pond extends battery, can effectively expand solid state battery in the application in the fields such as the energy, environmental protection.
Solid state battery provided by the invention has the polymer-modified layer of poly-dopamine, with large surface area, Neng Gouyu
Solid electrolyte surface and positive electrode surface are come into full contact in solid state battery, also further can be reduced anode by deformation and filled
The influence that volume change in discharge process contacts electrode/electrolyte interface, interfacial contact, reduction circle so as to improve battery
Face impedance, the cycle performance and service life for promoting battery.After the present invention uses the polymer-modified layer of poly-dopamine, assembling is consolidated
The cyclical stability and service life of state battery are significantly improved.In addition, preparation method provided by the invention is simple and efficient, fit
In large-scale application.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the SEM image of the polymer-modified layer surface pattern of poly-dopamine prepared by the embodiment of the present invention 1；
Fig. 2 is cycle performance curve and coulombic efficiency of the solid state battery under 0.1C current density in the embodiment of the present invention 1
Curve graph；
Fig. 3 is cycle performance curve and coulombic efficiency of the solid state battery under 0.1C current density in the embodiment of the present invention 2
Curve graph；
Fig. 4 is cycle performance curve and coulombic efficiency of the solid state battery under 0.1C current density in the embodiment of the present invention 3
Curve graph；
Fig. 5 is cycle performance curve and coulombic efficiency of the solid state battery under 0.1C current density in the embodiment of the present invention 4
Curve graph；
Fig. 6 is cycle performance curve and coulombic efficiency of the solid state battery under 0.1C current density in the embodiment of the present invention 5
Curve graph；
Fig. 7 is cycle performance curve and coulombic efficiency of the solid state battery under 0.1C current density in the embodiment of the present invention 6
Curve graph；
Fig. 8 is cycle performance curve and coulombic efficiency of the solid state battery under 0.1C current density in the embodiment of the present invention 7
Curve graph；
Fig. 9 is cycle performance curve and coulombic efficiency of the solid state battery under 0.1C current density in the embodiment of the present invention 8
Curve graph；
Figure 10 is cycle performance curve and coulombic efficiency of the solid state battery under 0.1C current density in comparative example 1 of the present invention
Curve graph；
Figure 11 is cycle performance curve and coulombic efficiency of the solid state battery under 0.1C current density in comparative example 2 of the present invention
Curve graph；
Figure 12 is cycle performance curve and coulombic efficiency of the solid state battery under 0.1C current density in comparative example 3 of the present invention
Curve graph.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Raw materials used following embodiment of the present invention is commercial goods, and electrolyte sheet used is that Hefei section crystalline substance material technology has
What limit company provided, Dopamine hydrochloride used is what Aladdin company provided, and positive electrode used is the refined green wood in Hunan
Expect what Co., Ltd provided, solid electrolyte powder is what Ke Jing Materials Technology Ltd. in Hefei provided, and conductive agent is that Nanjing is first
What the companies such as rich Nono-material Science & Technology Ltd. provided, negative electrode material is Sigma-Aldrich, can lithium industry in Tianjin
What Co., Ltd provided.
Embodiment 1
By with a thickness of the NASICON solid electrolyte sheet surface polishing of 0.6mm, cleans and be dried for standby in ethyl alcohol.It will
Trishydroxymethylaminomethane, which is dissolved in ethyl alcohol, stirs 2h to solution uniform, that obtained concentration is 0.1mol/L.Again to 100ml
20mg Dopamine hydrochloride is added in above-mentioned solution, is put into above-mentioned solid electrolyte sheet after mixing evenly, the insulated and stirred at 50 DEG C
12h is to complete the growth of solid electrolyte sheet surface polymer decorative layer.Then take out the electrolyte with polymer-modified layer
Piece is put into drying box afterwards wash with distilled water, and the dry 12h at 80 DEG C completes the preparation of poly-dopamine decorative layer, obtains compound
Solid electrolyte sheet.
By positive electrode FeS2, NASICON solid electrolyte powder, conductive agent Super P, binder EC according to mass ratio be
50:25:15:10 mixing is added terpinol as solvent, is mixed and made into anode sizing agent.Above-mentioned anode sizing agent is coated uniformly on
Above-mentioned composite solid electrolyte piece has the surface of poly-dopamine layer, and dries 12h at 80 DEG C.By above-mentioned painting coated positive pole material
Composite solid electrolyte piece be transferred in inert-atmosphere glove box, and be in the another side load thickness of complex solid electrolytic strip
The metal Na piece of 0.5mm, is assembled into battery and seals, obtain solid state battery.
SEM detection, testing result are carried out to the poly-dopamine layer of composite solid electrolyte piece prepared by the embodiment of the present invention 1
As shown in Figure 1, as shown in Figure 1, the polymer-modified layer of poly-dopamine is uniformly grown on the crystal grain on electrolyte sheet surface.
Solid state battery prepared by the embodiment of the present invention 1 carries out electrochemistry using blue electricity CT2001A battery test system
It can test, the voltage range of charge and discharge is 0.8~3.0V, and temperature is 60 DEG C, current density 0.1C, then carries out permanent multiplying power and fills
Electric discharge, evaluation recycle 50 discharge capacitances and coulombic efficiencies, and testing result is as shown in Fig. 2, can from Fig. 2
Out, the solid state battery of the solid electrolyte sheet preparation by this with poly-dopamine decorative layer is under 60 DEG C, 0.1C current density
First discharge specific capacity be 460.3mAh/g, initial charge specific capacity be 251.9mAh/g.Putting after cycle charge-discharge 50 times
Electric specific capacity is 149.0mAh/g, charge specific capacity 148.7mAh/g, coulombic efficiency 99.83%.After stable circulation, electricity
Tankage conservation rate is higher.
Embodiment 2
By with a thickness of the NASICON solid electrolyte sheet surface polishing of 0.4mm, cleans and be dried for standby in ethyl alcohol.It will
Cetyl trimethylammonium bromide, which is dissolved in distilled water, stirs 2h to solution uniform, that obtained concentration is 0.05mol/L.Again to
10mg Dopamine hydrochloride is added in the above-mentioned solution of 100ml, is put into above-mentioned solid electrolyte sheet after mixing evenly, is kept the temperature at 60 DEG C
10h is stirred to complete the growth of solid electrolyte sheet surface polymer decorative layer.Then take out consolidating with polymer-modified layer
Body electrolyte sheet, is put into drying box afterwards wash with distilled water, and the dry 12h at 80 DEG C completes the preparation of poly-dopamine decorative layer,
Obtain composite solid electrolyte piece.
By positive electrode FeS2, NASICON solid electrolyte powder, conductive agent acetylene black, binder PVDF is according to mass ratio
For 50:30:15:5 mixing, NMP is added as solvent, is mixed and made into anode sizing agent.Above-mentioned anode sizing agent is coated uniformly on
The surface that composite solid electrolyte piece has poly-dopamine layer, coating thickness 0.2mm are stated, and dries 12h at 80 DEG C.It will be upper
The composite solid electrolyte piece for stating coating anode sizing agent is transferred in inert-atmosphere glove box, and in composite solid electrolyte piece
Another side load thickness is the metal Na piece of 0.4mm, is assembled into battery and seals, obtains solid state battery.
Solid state battery prepared by the embodiment of the present invention 2 carries out electrochemistry using blue electricity CT2001A battery test system
It can test, the voltage range of charge and discharge is 0.8~3.0V, and temperature is 60 DEG C, current density 0.1C, then carries out permanent multiplying power and fills
Electric discharge, evaluation recycle 50 discharge capacitances and coulombic efficiencies, and testing result is as shown in figure 3, can from Fig. 3
Out, the solid state battery of the solid electrolyte sheet preparation by this with polymer-modified layer is under 60 DEG C, 0.1C current density
First discharge specific capacity is 320.5mAh/g, and initial charge specific capacity is 182.0mAh/g.Electric discharge after cycle charge-discharge 50 times
Specific capacity is 163.0mAh/g, charge specific capacity 162.1mAh/g, coulombic efficiency 99.44%.After stable circulation, battery
Capacity retention ratio is higher.
Embodiment 3
By with a thickness of the NASICON solid electrolyte sheet surface polishing of 0.8mm, cleans and be dried for standby in ethyl alcohol.It will
Trishydroxymethylaminomethane, which is dissolved in isopropanol, stirs 2h to solution uniform, that obtained concentration is 0.2mol/L.Again to
20mg Dopamine hydrochloride is added in the above-mentioned solution of 100ml, is put into above-mentioned solid electrolyte sheet after mixing evenly, is kept the temperature at 70 DEG C
6h is stirred to complete the growth of solid electrolyte sheet surface polymer decorative layer.Then take out the solid with polymer-modified layer
Electrolyte sheet is put into drying box afterwards wash with distilled water, and the dry 12h at 80 DEG C completes the preparation of poly-dopamine decorative layer, obtains
To composite solid electrolyte piece.
By positive electrode Fe1-xS, NASICON solid electrolyte powder, conductive agent Super P, binder CMC are according to mass ratio
For 50:20:20:10 mixing, NMP is added as solvent, is mixed and made into anode sizing agent.Above-mentioned anode sizing agent is coated uniformly on
The surface that composite solid electrolyte piece has poly-dopamine layer, coating thickness 0.15mm are stated, and dries 12h at 80 DEG C.It will
The composite solid electrolyte piece of above-mentioned coating anode sizing agent is transferred in inert-atmosphere glove box, and in composite solid electrolyte piece
Another side load thickness be 0.5mm metal Na piece, be assembled into battery and seal, obtain solid state battery.
Solid state battery prepared by the embodiment of the present invention 3 carries out electrochemistry using blue electricity CT2001A battery test system
It can test, the voltage range of charge and discharge is 0.5~3.0V, and temperature is 60 DEG C, current density 0.1C, then carries out permanent multiplying power and fills
Electric discharge, evaluation recycle 50 discharge capacitances and coulombic efficiencies, and testing result is as shown in figure 4, can from Fig. 4
Out, the solid state battery of the solid electrolyte sheet preparation by this with polymer-modified layer is under 60 DEG C, 0.1C current density
First discharge specific capacity is 518.3mAh/g, and initial charge specific capacity is 320.0mAh/g.Electric discharge after cycle charge-discharge 50 times
Specific capacity is 215.0mAh/g, charge specific capacity 214.2mAh/g, coulombic efficiency 99.61%.After stable circulation, battery
Capacity retention ratio is higher.
Embodiment 4
By with a thickness of the NASICON solid electrolyte sheet surface polishing of 0.5mm, cleans and be dried for standby in ethyl alcohol.It will
Polyvinyl alcohol, which is dissolved in distilled water, stirs 2h to solution uniform, that obtained concentration is 0.2mol/L.Again to the above-mentioned solution of 100ml
Middle addition 20mg Dopamine hydrochloride, is put into above-mentioned solid electrolyte sheet, insulated and stirred 10h is at 80 DEG C to complete after mixing evenly
The growth of solid electrolyte sheet surface polymer decorative layer.The solid electrolyte sheet with polymer-modified layer is then taken out, is used
It is put into drying box after distilled water cleaning, the dry 12h at 80 DEG C completes the preparation of poly-dopamine decorative layer, obtains complex solid
Electrolyte sheet.
By positive electrode FeS2, NASICON solid electrolyte powder, conductive agent graphene, binder SA according to mass ratio be
55:20:15:10 mixing is added terpinol as solvent, is mixed and made into anode sizing agent.Above-mentioned anode sizing agent is coated uniformly on
Above-mentioned composite solid electrolyte piece has the surface of poly-dopamine layer, coating thickness 0.3mm, and dries 12h at 80 DEG C.It will
The composite solid electrolyte piece of above-mentioned coating anode sizing agent is transferred in inert-atmosphere glove box, and in composite solid electrolyte piece
Another side load thickness be 0.3mm metal Na piece, be assembled into battery and seal, obtain solid state battery.
Solid state battery prepared by the embodiment of the present invention 4 carries out electrochemistry using blue electricity CT2001A battery test system
It can test, the voltage range of charge and discharge is 0.8~3.0V, and temperature is 60 DEG C, current density 0.1C, then carries out permanent multiplying power and fills
Electric discharge, evaluation recycle 50 discharge capacitances and coulombic efficiencies, and testing result is as shown in figure 5, can from Fig. 5
Out, the solid state battery of the solid electrolyte sheet preparation by this with polymer-modified layer is under 60 DEG C, 0.1C current density
First discharge specific capacity is 417.8mAh/g, and initial charge specific capacity is 267.6mAh/g.Electric discharge after cycle charge-discharge 50 times
Specific capacity is 205.0mAh/g, charge specific capacity 203.2mAh/g, coulombic efficiency 99.11%.After stable circulation, battery
Capacity retention ratio is higher.
Embodiment 5
By with a thickness of the Garnet solid electrolyte sheet surface polishing of 1mm, cleans and be dried for standby in ethyl alcohol.By three hydroxyls
Vlmethyl methane, which is dissolved in distilled water, stirs 2h to solution uniform, that obtained concentration is 0.2mol/L.Again on 100ml
Addition 25mg Dopamine hydrochloride in solution is stated, is put into above-mentioned solid electrolyte sheet after mixing evenly, the insulated and stirred 12h at 80 DEG C
To complete the growth of solid electrolyte sheet surface polymer decorative layer.Then take out the solid electrolyte with polymer-modified layer
Piece is put into drying box afterwards wash with distilled water, and the dry 12h at 80 DEG C completes the preparation of poly-dopamine decorative layer, obtains compound
Solid electrolyte sheet.
By positive electrode LiFePO4, Garnet solid electrolyte powder, conductive agent Super P, binder EC is according to mass ratio
For 60:20:10:10 mixing, terpinol is added as solvent, is mixed and made into anode sizing agent.Above-mentioned anode sizing agent is uniformly coated
The surface of poly-dopamine layer, coating thickness 0.1mm are had in above-mentioned composite solid electrolyte piece, and dries 12h at 80 DEG C.
The composite solid electrolyte piece of above-mentioned painting coated positive pole material is transferred in inert-atmosphere glove box, and in composite solid electrolyte
The another side load thickness of piece is the metal Li piece of 0.2mm, is assembled into battery and seals, obtains solid state battery.
Solid state battery prepared by the embodiment of the present invention 5 carries out electrochemistry using blue electricity CT2001A battery test system
It can test, the voltage range of charge and discharge is 2.8~3.8V, and temperature is 60 DEG C, current density 0.1C, then carries out permanent multiplying power and fills
Electric discharge, evaluation recycle 50 discharge capacitances and coulombic efficiencies, and testing result is as shown in fig. 6, can from Fig. 6
Out, the solid state battery of the solid electrolyte sheet preparation by this with polymer-modified layer is under 60 DEG C, 0.1C current density
Initial charge specific capacity is 145.2mAh/g, first discharge specific capacity 144.6mAh/g.Charging after cycle charge-discharge 50 times
Specific capacity is 140.7mAh/g, specific discharge capacity 140.2mAh/g, coulombic efficiency 99.64%.After stable circulation, battery
Capacity retention ratio is higher.
Embodiment 6
By with a thickness of the Garnet solid electrolyte sheet surface polishing of 1mm, cleans and be dried for standby in ethyl alcohol.By 16
Alkyl trimethyl ammonium bromide, which is dissolved in isopropanol, stirs 2h to solution uniform, that obtained concentration is 0.1mol/L.Again to 100ml
15mg Dopamine hydrochloride is added in above-mentioned solution, is put into above-mentioned solid electrolyte sheet after mixing evenly, the insulated and stirred at 60 DEG C
6h is to complete the growth of solid electrolyte sheet surface polymer decorative layer.Then take out the solid electrolytic with polymer-modified layer
Matter piece, is put into drying box afterwards wash with distilled water, and the dry 12h at 80 DEG C completes the preparation of poly-dopamine decorative layer, answered
Close solid electrolyte sheet.
By positive electrode LiCoO2, Garnet solid electrolyte powder, carbon nanotube, binder PVDF according to mass ratio be
70:15:10:5 mixing is added terpinol as solvent, is mixed and made into anode sizing agent.Above-mentioned anode sizing agent is coated uniformly on
Composite solid electrolyte on piece, coating thickness 0.3mm are stated, and dries 12h at 80 DEG C.By answering for above-mentioned coating anode sizing agent
It closes solid electrolyte sheet to be transferred in inert-atmosphere glove box, and is in composite solid electrolyte piece another side load thickness
The Li-In alloy anode of 0.6mm, is assembled into battery and seals, obtain solid state battery.
Solid state battery prepared by the embodiment of the present invention 6 carries out electrochemistry using blue electricity CT2001A battery test system
It can test, the voltage range of charge and discharge is 2.5~3.6V, and temperature is room temperature, then current density 0.1C carries out permanent multiplying power and fills
Electric discharge, evaluation recycle 50 discharge capacitances and coulombic efficiencies, and testing result is as shown in fig. 7, can from Fig. 7
Out, the solid state battery of the solid electrolyte sheet preparation by this with polymer-modified layer is under 60 DEG C, 0.1C current density
Initial charge specific capacity is 81.6mAh/g, first discharge specific capacity 72mAh/g.Charging specific volume after cycle charge-discharge 50 times
Amount is 95.9mAh/g, specific discharge capacity 95.6mAh/g, coulombic efficiency 99.69%.After stable circulation, battery capacity is protected
Holdup is higher.
Embodiment 7
By with a thickness of the Garnet solid electrolyte sheet surface polishing of 1mm, cleans and be dried for standby in ethyl alcohol.By three hydroxyls
Vlmethyl methane, which is dissolved in isopropanol, stirs 2h to solution uniform, that obtained concentration is 0.3mol/L.Again on 100ml
Addition 25mg Dopamine hydrochloride in solution is stated, is put into above-mentioned solid electrolyte sheet after mixing evenly, the insulated and stirred 4h at 50 DEG C
To complete the growth of solid electrolyte sheet surface polymer decorative layer.Then take out the solid electrolyte with polymer-modified layer
Piece is put into drying box afterwards wash with distilled water, and the dry 12h at 80 DEG C completes the preparation of poly-dopamine decorative layer, obtains compound
Solid electrolyte sheet.
By positive electrode NCA, Garnet solid electrolyte powder, Ketjen black, binder PVDF according to mass ratio be 65:
20:10:5 mixing is added NMP as solvent, is mixed and made into anode sizing agent.Above-mentioned anode sizing agent is coated uniformly on above-mentioned compound
Solid electrolyte sheet has the surface of poly-dopamine layer, coating thickness 0.4mm, and dries 12h at 80 DEG C.By above-mentioned coating
Composite solid electrolyte piece is transferred in inert-atmosphere glove box, and is in the another side load thickness of composite solid electrolyte piece
The Li-In alloy anode of 0.5mm, is assembled into battery and seals, obtain solid state battery.
Solid state battery prepared by the embodiment of the present invention 7 carries out electrochemistry using blue electricity CT2001A battery test system
It can test, the voltage range of charge and discharge is 2.5~3.6V, and temperature is room temperature, then current density 0.1C carries out permanent multiplying power and fills
Electric discharge, evaluation recycle 50 discharge capacitances and coulombic efficiencies, and testing result is as shown in figure 8, can from Fig. 8
Out, the solid state battery of the solid electrolyte sheet preparation by this with polymer-modified layer is under 60 DEG C, 0.1C current density
Initial charge specific capacity is 104.4mAh/g, first discharge specific capacity 81.6mAh/g.Charge ratio after cycle charge-discharge 50 times
Capacity is 71.6mAh/g, specific discharge capacity 70.7mAh/g, coulombic efficiency 98.74%.After stable circulation, battery capacity
Conservation rate is higher.
Embodiment 8
By with a thickness of the NASICON solid electrolyte sheet surface polishing of 0.5mm, cleans and be dried for standby in ethyl alcohol.It will
Polyvinyl alcohol, which is dissolved in the water, stirs 2h to solution uniform, that obtained concentration is 0.3mol/L.Add again into the above-mentioned solution of 100ml
Enter 15mg Dopamine hydrochloride, be put into above-mentioned solid electrolyte sheet after mixing evenly, insulated and stirred 8h is at 80 DEG C to complete solid
The growth of electrolyte sheet surface polymer decorative layer.The solid electrolyte sheet with polymer-modified layer is then taken out, with distillation
It is put into drying box after water cleaning, the dry 12h at 80 DEG C completes the preparation of poly-dopamine decorative layer, obtains complex solid electrolysis
Matter piece.
By positive electrode Na3V2(PO4)3, NASICON solid electrolyte powder, acetylene black, binder EC according to mass ratio be
55:25:10:10 mixing is added terpinol as solvent, is mixed and made into anode sizing agent.Above-mentioned anode sizing agent is coated uniformly on
Above-mentioned composite solid electrolyte piece has the surface of poly-dopamine layer, coating thickness 0.25mm, and dries 12h at 80 DEG C.
The composite solid electrolyte piece of above-mentioned coating anode sizing agent is transferred in inert-atmosphere glove box, and in composite solid electrolyte
The another side load thickness of piece is the metal Na piece of 0.4mm, is assembled into battery and seals, obtains solid state battery.
Solid state battery prepared by the embodiment of the present invention 8 carries out electrochemistry using blue electricity CT2001A battery test system
It can test, the voltage range of charge and discharge is 2.5~4.0V, and temperature is room temperature, then current density 0.1C carries out permanent multiplying power and fills
Electric discharge, evaluation recycle 50 discharge capacitances and coulombic efficiencies, and testing result is as shown in figure 9, can from Fig. 9
Out, the solid state battery of the solid electrolyte sheet preparation by this with polymer-modified layer is under 60 DEG C, 0.1C current density
Initial charge specific capacity is 87.3mAh/g, first discharge specific capacity 79.2mAh/g.Charge ratio after cycle charge-discharge 50 times
Capacity is 66.0mAh/g, specific discharge capacity 65.7mAh/g, coulombic efficiency 99.55%.After stable circulation, battery capacity
Conservation rate is higher.
Comparative example 1
By with a thickness of the NASICON solid electrolyte sheet surface polishing of 0.5mm, cleans and be dried for standby in ethyl alcohol.It will
Positive electrode FeS2, NASICON solid electrolyte powder, conductive agent Super P, binder CMC according to mass ratio be 50:25:20:
5 mixing are added NMP as solvent, are mixed and made into anode sizing agent.Above-mentioned anode sizing agent is coated uniformly on above-mentioned without modification
The solid electrolyte on piece of processing, coating thickness 0.2mm, and 12h is dried at 80 DEG C.The electrolyte of coated positive pole material will be applied
Piece is transferred in inert-atmosphere glove box, and in the metal Na piece that the another side load thickness of electrolyte sheet is 0.5mm, is assembled into
Battery simultaneously seals, and obtains solid state battery.
Solid state battery prepared by comparative example 1 of the present invention carries out electrochemistry using blue electricity CT2001A battery test system
It can test, the voltage range of charge and discharge is 0.8~3.0V, and temperature is 60 DEG C, current density 0.1C, then carries out permanent multiplying power and fills
Electric discharge, evaluation recycle 50 discharge capacitances and coulombic efficiencies, and testing result is as shown in Figure 10, can from Figure 10
Out, the solid state battery of the solid electrolyte sheet preparation by this without polymer-modified layer is under 60 DEG C, 0.1C current density
First discharge specific capacity is 453.3mAh/g, and initial charge specific capacity is 315.8mAh/g.Electric discharge after cycle charge-discharge 50 times
Specific capacity is 99.1mAh/g, charge specific capacity 89.9mAh/g, coulombic efficiency 90.65%.Battery is circulated throughout for a long time
There are obvious capacity attenuation in journey, cyclical stability is poor, and coulombic efficiency reduces.
Comparative example 2
By with a thickness of the NASICON solid electrolyte sheet surface polishing of 0.6mm, cleans and be dried for standby in ethyl alcohol.It will
Positive electrode FeS2, NASICON solid electrolyte powder, conductive agent Ketjen black, binder PVDF according to mass ratio be 45:20:
25:10 mixing is added NMP as solvent, is mixed and made into anode sizing agent.By above-mentioned anode sizing agent be coated uniformly on it is above-mentioned without
The solid electrolyte on piece of moditied processing, coating thickness 0.15mm, and 12h is dried at 80 DEG C.Above-mentioned coating anode is starched
The electrolyte sheet of material is transferred in inert-atmosphere glove box, and in the metal that the another side load thickness of electrolyte sheet is 0.5mm
Na piece is assembled into battery and seals, obtains solid state battery.
Solid state battery prepared by comparative example 2 of the present invention carries out electrochemistry using blue electricity CT2001A battery test system
It can test, the voltage range of charge and discharge is 0.8~3.0V, and temperature is 60 DEG C, current density 0.1C, then carries out permanent multiplying power and fills
Electric discharge, evaluation recycle 50 discharge capacitances and coulombic efficiencies, and testing result is as shown in figure 11, can from Figure 11
Out, the solid state battery of the solid electrolyte sheet preparation by this without polymer-modified layer is under 60 DEG C, 0.1C current density
First discharge specific capacity is 390.0mAh/g, and initial charge specific capacity is 295.4mAh/g.Electric discharge after cycle charge-discharge 50 times
Specific capacity is 55.8mAh/g, charge specific capacity 53.6mAh/g, coulombic efficiency 96.09%.Battery is circulated throughout for a long time
There are obvious capacity attenuation in journey, cyclical stability is poor, and coulombic efficiency reduces.
Comparative example 3
By with a thickness of the NASICON solid electrolyte sheet surface polishing of 0.7mm, cleans and dry in ethyl alcohol, be transferred to
In inert-atmosphere glove box.PEO is dissolved in acetonitrile, according to EO base: Li+The ratio of=18:1 by electric conducting lithium salt LiTFSI with
PEO is mixed and stirred for uniformly.PEO solution is coated uniformly on solid electrolyte sheet surface and is dried, coating thickness 0.3mm,
PEO layer preparation is completed, composite solid electrolyte piece is obtained.By positive electrode FeS2, NASICON solid electrolyte powder, conductive agent
Carbon nanotube, binder PVDF are 65:15:15:5 mixing according to mass ratio, and NMP is added as solvent, is mixed and made into positive slurry
Material.Above-mentioned anode sizing agent is coated uniformly on the above-mentioned solid electrolyte on piece without moditied processing, coating thickness is
0.25mm, and 12h is dried at 80 DEG C.It is 0.5mm by the another side load thickness of the electrolyte sheet of above-mentioned coating anode sizing agent
Metal Na piece, be assembled into battery and seal, obtain solid state battery.
Solid state battery prepared by comparative example 3 of the present invention carries out electrochemistry using blue electricity CT2001A battery test system
It can test, the voltage range of charge and discharge is 0.8~3.0V, and temperature is 60 DEG C, current density 0.1C, then carries out permanent multiplying power and fills
Electric discharge, evaluation recycle 50 discharge capacitances and coulombic efficiencies, and testing result is as shown in figure 12, can from Figure 12
Out, the solid state battery of the solid electrolyte sheet preparation by this without polymer-modified layer is under 60 DEG C, 0.1C current density
First discharge specific capacity is 372.3mAh/g, and initial charge specific capacity is 355.4mAh/g.Electric discharge after cycle charge-discharge 50 times
Specific capacity is 155.5mAh/g, charge specific capacity 154.2mAh/g, coulombic efficiency 99.17%.Battery is recycled in long-time
There is obvious capacity attenuation in the process.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (10)
1. a kind of composite solid electrolyte piece, comprising:
Electrolyte sheet；
The poly-dopamine layer on the electrolyte sheet surface is set.
2. composite solid electrolyte piece according to claim 1, which is characterized in that the material of the electrolyte sheet is selected from
One in the solid electrolyte of NASICON structure, the solid electrolyte of Garnet structure and the solid electrolyte of perovskite structure
Kind is several.
3. composite solid electrolyte piece according to claim 1, which is characterized in that the poly-dopamine layer with a thickness of 2
~500nm.
4. a kind of preparation method of composite solid electrolyte piece, comprising:
Dopamine hydrochloride, auxiliary agent and solvent are mixed, dopamine polymeric solution is obtained；
It is dry after the dopamine polymeric solution and electrolyte sheet are mixed, obtain composite solid electrolyte piece.
5. according to the method described in claim 4, it is characterized in that, the auxiliary agent is selected from trishydroxymethylaminomethane, 16
Alkyl trimethyl ammonium bromide or polyvinyl alcohol.
6. according to the method described in claim 4, it is characterized in that, the solvent is selected from water, ethyl alcohol or isopropanol.
7. a kind of solid state battery, comprising: negative electrode material, composite solid electrolyte piece and anode composite.
8. solid state battery according to claim 7, which is characterized in that the anode composite includes:
Positive electrode, solid electrolyte powder, conductive additive and binder.
9. solid state battery according to claim 8, which is characterized in that the positive electrode is selected from FeS2、Fe1-xS、WS2、
Na3V2(PO4)3、LiCoO2、LiFePO4, NCM or NCA；
The conductive additive is selected from one or more of Ketjen black, acetylene black, Super P, carbon nanotube and graphene.
10. solid state battery according to claim 8, which is characterized in that the binder is selected from ethyl cellulose, gathers inclined fluorine
One or more of ethylene, sodium alginate and sodium carboxymethylcellulose.
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| CN112909328A (en) * | 2019-12-04 | 2021-06-04 | 中国科学院宁波材料技术与工程研究所 | Ultrathin sulfide solid electrolyte layer and preparation method and application thereof |
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