CN109037764A - A kind of preparation method of the solid electrolyte of stable lithium an- ode - Google Patents
A kind of preparation method of the solid electrolyte of stable lithium an- ode Download PDFInfo
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- CN109037764A CN109037764A CN201810995804.8A CN201810995804A CN109037764A CN 109037764 A CN109037764 A CN 109037764A CN 201810995804 A CN201810995804 A CN 201810995804A CN 109037764 A CN109037764 A CN 109037764A
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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
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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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
- H01M2300/0068—Solid electrolytes inorganic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A kind of preparation method of the solid electrolyte of stable lithium an- ode includes the following steps: (1) by inorganic molecules mortar grinder at powder, glove box preservation；The inorganic molecules are selected from LiF, LiOH, Li2S、LiCl、LiBr、LiI、Li2O、Li2CO3、LiNO3One of or it is a variety of；(2) polymeric matrix, lithium salts and inorganic molecules powder are dissolved in anhydrous acetonitrile according to a certain percentage, homogeneous solution is stirred at room temperature to obtain；The quality dosage of the inorganic molecules particle is the 1-20% of polymeric matrix and lithium salts gross mass；It is completely dried it resulting homogeneous solution volatilization of step (2), obtains solid electrolyte.Preparation method simple process of the present invention is feasible, at low cost, is suitble to large-scale production, and obtained solid electrolyte can effectively inhibit the growth of Li dendrite, improve the coulombic efficiency and cycle performance of battery.
Description
(1) technical field
The invention belongs to solid lithium ion battery technical fields, are related to a kind of solid electrolyte of stable lithium an- ode
Preparation method.
(2) background technique
Lithium metal is due to its high theoretical capacity (3860mAh g-1) and low reduction potential (- 3.04V) be considered as very
Promising negative electrode material, but cathode of lithium the problems such as there is dendritic growth and nonuniform depositions so that its practical application by
To limitation.In cyclic process, the growth of Li dendrite can destroy lithium surface SEI film, and duplicate rupture and growth SEI can be continuous
Fresh lithium and electrolyte are consumed, the cycle life of low coulombic efficiency, high polarizing voltage and difference is caused.Further,
Li dendrite can pierce through diaphragm, lead to the failure of battery.In view of the above technical problems, adding in the electrolytic solution some can regulate and control
The material of SEI component is effective solution method, can form uniform SEI, can regulate and control the depositing behavior of lithium, is effectively inhibited
Dendrite.But the problems such as in view of the inflammable of electrolyte, volatilization, solid electrolyte can be used instead of liquid electrolyte.Solid state electrolysis
Matter can be arbitrarily bent, and folded, be suitble to the application of extensive soft-package battery and flexible battery；And environmentally friendly, cost
It is low.
Conventional solid electrolyte is for inhibiting Li dendrite to play huge effect.But due to its own mechanical performance
With the influence of component, there are also very big rooms for promotion.Composite solid electrolyte is prepared to further decrease polarization, promotes cyclicity
It can be most important.
(3) summary of the invention
It is feasible that goal of the invention of the invention is to provide a kind of simple process, at low cost, is suitble to the stabilization lithium of large-scale production
The preparation method of the solid electrolyte of metal negative electrode improves the coulombic efficiency of battery and follows effectively to inhibit the growth of Li dendrite
Ring performance and high rate performance.
Technical solution of the present invention is specifically described below.
The present invention provides a kind of preparation methods of the solid electrolyte of stable lithium an- ode, include the following steps:
(1) by inorganic molecules mortar grinder at powder, glove box is saved；
The inorganic molecules are selected from LiF, LiOH, Li2S、LiCl、LiBr、LiI、Li2O、Li2CO3、LiNO3In one
Kind is a variety of；
(2) polymeric matrix, lithium salts and inorganic molecules powder are dissolved in anhydrous acetonitrile according to a certain percentage, room temperature
Stir to obtain homogeneous solution；
The quality dosage of the inorganic molecules particle is the 1-20% of polymeric matrix and lithium salts gross mass；
(3) it is completely dried it resulting homogeneous solution volatilization of step (2), obtains solid electrolyte.
In preparation process of the present invention, water and oxygen content in lithium salts use environment need to be controlled and be less than 10ppm.
In step (1) of the present invention, preferred inorganic molecules are LiF, LiOH, Li2One or more of S.
In step (2) of the present invention, the preferred polyethylene glycol oxide of the polymeric matrix (PEO), the lithium salts is double three
Methyl fluoride sulfimide lithium (LiTFSI), lithium perchlorate (LiClO4), di-oxalate lithium borate (LiBOB) or bis- (fluorine sulphonyl) imines
Lithium (LiFSI).The mass ratio of the polyethylene glycol oxide and lithium salts is EO:Li+=10-20:1, preferably 15:1.It is preferred inorganic
The quality dosage of small molecule is the 5-10% of polymeric matrix and lithium salts gross mass.
In step (2) of the present invention, the polymer P EO, lithium salts, inorganic molecules particle need to carry out respectively before use
It is dry, preferably 50 DEG C, 120 DEG C, 80 DEG C of dryings for 24 hours, obtain dry polymeric matrix, lithium salts and inorganic molecules particle.
In step (2) of the present invention, the time being stirred at room temperature is 24-48h, preferably for 24 hours.
In step (3) of the present invention, solution volatilizees 2-12h (preferably 6h) in room temperature first, then is placed in 50-60 DEG C (preferably 50
DEG C) 12-24h (preferably 12h) is volatilized on warm table.
In step (3) of the present invention, those skilled in the art can control solid polymer electrolyte according to actual needs
Thickness.
The solid electrolyte of stable lithium an- ode provided by the invention can be used for all solid lithium metal battery.
The principle of the present invention is: solid electrolyte can change the depositing behavior of lithium first, make the difficult long dendrite of cathode of lithium；Its
Secondary, the addition of inorganic molecules can regulate and control the component of lithium surface SEI, make inorganic LiF, LiOH, Li2S、Li2S2Etc. components contain
Amount increases, and keeps the mechanical performance of SEI stronger, thus dendrite inhibition.
Beneficial effects of the present invention are as follows:
(1) for the present invention using addition strategy, entire simple process is feasible, at low cost, is suitble to large-scale industrialization.Raw material
Toxicity is low, safety and environmental protection.
(2) composite solid electrolyte provided by the present invention can effectively inhibit the growth of Li dendrite, improve battery
Coulombic efficiency and cycle performance and high rate performance.
(4) Detailed description of the invention
Fig. 1 is PEO-Li-Li prepared by the embodiment of the present invention 12The Optical Morphology of S solid electrolyte membrane.
Fig. 2 is the performance that PEO-Li solid electrolyte prepared by comparative example 1 of the present invention is used for the test of lithium symmetrical cycle, electric current
Density: 0.1mA cm-1, capacity: 0.1mAh cm-1。
Fig. 3 is PEO-Li-Li prepared by the embodiment of the present invention 12S solid electrolyte is used for the property of lithium symmetrical cycle test
Can, current density: 0.1mA cm-1, capacity: 0.1mAh cm-1。
Fig. 4 is the performance that PEO-Li-LiF solid electrolyte prepared by the embodiment of the present invention 2 is used for the test of lithium symmetrical cycle,
Current density: 0.1mA cm-1, capacity: 0.1mAh cm-1。
Fig. 5 is that comparative example 2 and embodiment 2 of the present invention prepare consolidating based on PEO-Li and PEO-Li-LiF solid electrolyte
The high rate performance of state lithium metal battery, charging/discharging voltage range 2.5-3.8V, positive LiFePO4, current density: 0.2,0.4,
0.8,1.0,2.0C (1.0C=174mAh g-1)。
Fig. 6 is the property that PEO-Li-LiOH solid electrolyte prepared by the embodiment of the present invention 3 is used for the test of lithium symmetrical cycle
Can, current density: 0.1mA cm-1, capacity: 0.1mAh cm-1。
Fig. 7 is PEO-Li the and PEO-Li-LiOH solid electrolyte of comparative example 3 and embodiment 3 preparation of the present invention for lithium
Symmetrical cycle tests the SEM figure before and after 500h.(a) lithium surface before recycling, lithium surface (PEO-Li electrolyte) after (b) recycling, (c)
Lithium surface (PEO-Li-LiOH electrolyte) after circulation.
Based on Fig. 8 is comparative example 3 and embodiment 3 of the present invention preparation PEO-Li and PEO-Li-LiOH solid electrolyte
The high rate performance of solid-state lithium metal battery, charging/discharging voltage range 2.5-3.8V, positive LiFePO4, current density: 0.2,0.4,
0.8,1.0,2.0C (1.0C=174mAh g-1)。
Fig. 9 is PEO-Li-Li prepared by the embodiment of the present invention 42CO3Solid electrolyte is used for the property of lithium symmetrical cycle test
Can, current density: 0.1mA cm-1, capacity: 0.1mAh cm-1。
(5) specific implementation method
With specific embodiment, technical scheme is described further below, but protection scope of the present invention is unlimited
In this.
Embodiment 1
By Li2S powder, polymeric matrix PEO, lithium salts LiClO4Be respectively placed in 80 DEG C, 50 DEG C, 120 DEG C of dryings for 24 hours.Then
PEO and LiClO4By EO:Li+=15:1 is dissolved in anhydrous acetonitrile, by PEO and LiClO4Li is added in the 10wt% of gross mass2S powder
End is stirred at room temperature for 24 hours, forms homogeneous solution.Room temperature volatilization 6h, then 50 DEG C of warm tables volatilization 12h are placed in, uniformly it is electrolysed
Plasma membrane (PEO-Li-Li2S electrolyte).
Comparative example 1
Do not add Li2S powder, other obtain pure solid electrolyte (PEO-Li electrolyte) with embodiment 1.
Electrolyte is cut into the sequin of 19mm, attached drawing 1 is PEO-Li-Li2The Optical Morphology of S dielectric film, it is seen that electricity
The flexibility for solving plasma membrane is preferable, can arbitrarily be bent.
Solid electrolyte membrane (the PEO-Li-Li obtained by embodiment 1 and comparative example 12S, PEO-Li electrolyte) assembling
It is tested at lithium Symmetrical cells, wherein dielectric film both sides are the identical lithium pieces of size.It is tested at 50 DEG C, Li/
The polarizing voltage of PEO-Li/Li battery about 100mV, battery is stablized in preceding 300h to be recycled, and voltage sharply becomes smaller after 300h, battery
Start to deteriorate, such as attached drawing 2.And Li/PEO-Li-Li2The polarizing voltage of S/Li battery about 50mV, battery can stablize circulation
1000h, such as attached drawing 3.It can be seen that Li2The stability of lithium symmetrical cycle can be improved in S, illustrates PEO-Li-Li2S electrolyte is that one kind can
To stablize the electrolyte of lithium an- ode.
Embodiment 2
By LiF powder, polymeric matrix PEO, lithium salts LiTFSI be respectively placed in 80 DEG C, 50 DEG C, 120 DEG C of dryings for 24 hours.Then
PEO and LiTFSI presses EO:Li+=15:1 is dissolved in anhydrous acetonitrile, and LiF powder is added by the 10wt% of PEO and LiTFSI gross mass
End is stirred at room temperature for 24 hours, forms homogeneous solution.Room temperature volatilization 6h, then 50 DEG C of warm tables volatilization 12h are placed in, uniformly it is electrolysed
Plasma membrane (PEO-Li-LiF electrolyte), the sequin that electrolyte is cut into 19mm is stand-by.
Comparative example 2
LiF powder is not added, other obtain pure solid electrolyte (PEO-Li electrolyte) with embodiment 2.
The solid electrolyte membrane obtained by embodiment 2 and comparative example 2 (PEO-Li-LiF, PEO-Li electrolyte) is assembled into
Lithium Symmetrical cells are tested, and wherein dielectric film both sides are the identical lithium pieces of size.It is tested at 50 DEG C, Li/PEO-
The polarizing voltage of Li/Li battery about 100mV, battery is stablized in preceding 300h to be recycled, and voltage sharply becomes smaller after 300h, and battery starts
Deteriorate, such as attached drawing 2.And the polarizing voltage of Li/PEO-Li-LiF/Li battery about 55mV, battery can stablize circulation 1000h,
Such as attached drawing 4.It can be seen that the stability of lithium symmetrical cycle can be improved in LiF, illustrate that PEO-Li-LiF electrolyte is that one kind can be stablized
The electrolyte of lithium an- ode.
The solid electrolyte membrane obtained by embodiment 2 and comparative example 2 (PEO-Li-LiF, PEO-Li electrolyte) is by following
Method dresses up solid-state lithium metal battery.
LiFePO is weighed respectively with the mass ratio of 80:10:104: super-P:PVDF is coated in aluminium flake table after mixing evenly
Anode is made in face, 60 DEG C of vacuum drying 12h.By LiFePO4/ PEO-Li-LiF/Li or LiFePO4/ PEO-Li/Li assembling is helped
Solid-state lithium metal battery.Fig. 5 is corresponding solid state lithium battery at 50 DEG C, under 0.2,0.4,0.8,1.0,2.0C current density,
High rate performance curve in the voltage range of 2.5-3.8V.It can be seen that LiFePO4/ PEO-Li-LiF/Li battery has more excellent
Under different high rate performance, especially high current density, the promotion of performance is more obvious, hence it is evident that is better than LiFePO4/PEO-Li/Li
Battery.
Embodiment 3
By LiOH powder, polymeric matrix PEO, lithium salts LiClO4Be respectively placed in 80 DEG C, 50 DEG C, 120 DEG C of dryings for 24 hours.So
PEO and LiClO afterwards4By EO:Li+=10:1 is dissolved in anhydrous acetonitrile, by PEO and LiClO4LiOH powder is added in the 5wt% of gross mass
End is stirred at room temperature for 24 hours, forms homogeneous solution.Room temperature volatilization 6h, then 50 DEG C of warm tables volatilization 12h are placed in, uniformly it is electrolysed
Plasma membrane (PEO-Li-LiOH electrolyte), the sequin that electrolyte is cut into 19mm is stand-by.
Comparative example 3
LiOH powder is not added, other obtain pure solid electrolyte (PEO-Li electrolyte) with embodiment 3.
The solid electrolyte membrane obtained by embodiment 3 and comparative example 3 (PEO-Li-LiOH, PEO-Li electrolyte) assembling
It is tested at lithium Symmetrical cells, wherein dielectric film both sides are the identical lithium pieces of size.It is tested at 50 DEG C, Li/
The polarizing voltage of PEO-Li/Li battery about 100mV, battery is stablized in preceding 300h to be recycled, and voltage sharply becomes smaller after 300h, battery
Start to deteriorate, such as attached drawing 2.And the polarizing voltage of Li/PEO-Li-LiOH/Li battery about 60mV, battery can stablize circulation
1000h, such as attached drawing 6.It can be seen that the stability of lithium symmetrical cycle can be improved in LiOH.
The variation of lithium surface topography before and after observation lithium symmetrical cycle is characterized by SEM.Attached drawing 7a is lithium surface before recycling
Pattern, it can be seen that lithium surface is relative smooth and smooth.After recycling 500h, Li/PEO-Li/Li battery, lithium piece table are dismantled
Face becomes very uneven, there is many sharp little particles (attached drawing 7b).And the lithium surface of Li/PEO-Li-LiOH/Li battery is also
It is and recycles preceding close, very smooth (attached drawing 7c).Illustrate that PEO-Li-LiOH electrolyte is that one kind can stablize lithium an- ode
Electrolyte.
LiFePO is weighed respectively with the mass ratio of 80:10:104: super-P:PVDF is coated in aluminium flake table after mixing evenly
Anode is made in face, 60 DEG C of vacuum drying 12h.By LiFePO4/ PEO-Li-LiOH/Li or LiFePO4/ PEO-Li/Li is assembled into
All solid lithium metal battery.Fig. 8 is corresponding solid state lithium battery at 50 DEG C, under 0.2,0.4,0.8,1.0,2.0C current density,
High rate performance curve in the voltage range of 2.5-3.8V.It can be seen that LiFePO4/ PEO-Li-LiOH/Li battery has more excellent
Under different high rate performance, especially high current density, the charge/discharge capacity of battery is LiFePO42 times of/PEO-Li/Li battery,
Promote 100%.
Embodiment 4
By Li2CO3Powder, polymeric matrix PEO, lithium salts LiFSI be respectively placed in 80 DEG C, 50 DEG C, 120 DEG C of dryings for 24 hours.So
PEO and LiFSI presses EO:Li afterwards+=10:1 is dissolved in anhydrous acetonitrile, and Li is added by the 10wt% of PEO and LiFSI gross mass2CO3
36h is stirred at room temperature in powder, forms homogeneous solution.Room temperature volatilization 6h, then 50 DEG C of warm tables volatilization 12h are placed in, obtain uniform electricity
Solve plasma membrane (PEO-Li-Li2CO3Electrolyte), the sequin that electrolyte is cut into 19mm is stand-by.
Comparative example 4
Do not add Li2CO3Powder, other obtain pure solid electrolyte (PEO-Li electrolyte) with embodiment 4.
Solid electrolyte membrane (the PEO-Li-Li obtained by embodiment 4 and comparative example 42CO3, PEO-Li electrolyte) and assembling
It is tested at lithium Symmetrical cells, wherein dielectric film both sides are the identical lithium pieces of size.It is tested at 50 DEG C, Li/
The polarizing voltage of PEO-Li/Li battery about 100mV, battery is stablized in preceding 300h to be recycled, and voltage sharply becomes smaller after 300h, battery
Start to deteriorate, such as attached drawing 2.And Li/PEO-Li-Li2CO3The polarizing voltage about 70mV of/Li battery, battery can stablize circulation
600h, such as attached drawing 9.It can be seen that Li2CO3The stability of lithium symmetrical cycle can be improved.Illustrate PEO-Li-Li2CO3Electrolyte is one
Kind can stablize the electrolyte of lithium an- ode.
Embodiment 5
By LiNO3Powder, polymeric matrix PEO, lithium salts LiTFSI be respectively placed in 80 DEG C, 50 DEG C, 120 DEG C of dryings for 24 hours.So
PEO and LiTFSI presses EO:Li afterwards+=20:1 is dissolved in anhydrous acetonitrile, and LiNO is added by the 15wt% of PEO and LiTFSI gross mass3
36h is stirred at room temperature in powder, forms homogeneous solution.Room temperature volatilization 6h, then 50 DEG C of warm tables volatilization 12h are placed in, obtain uniform electricity
Solve plasma membrane (PEO-Li-LiNO3Electrolyte), the sequin that electrolyte is cut into 19mm is stand-by.
Comparative example 5
Do not add LiNO3Powder, other obtain pure solid electrolyte (PEO-Li electrolyte) with embodiment 5.
Claims (10)
1. a kind of preparation method of the solid electrolyte of stable lithium an- ode, includes the following steps:
(1) by inorganic molecules mortar grinder at powder, glove box is saved；
The inorganic molecules are selected from LiF, LiOH, Li2S、LiCl、LiBr、LiI、Li2O、Li2CO3、LiNO3One of or
It is a variety of；
(2) polymeric matrix, lithium salts and inorganic molecules powder are dissolved in anhydrous acetonitrile according to a certain percentage, are stirred at room temperature
Obtain homogeneous solution；
The quality dosage of the inorganic molecules particle is the 1-20% of polymeric matrix and lithium salts gross mass；
(3) it is completely dried it resulting homogeneous solution volatilization of step (2), obtains solid electrolyte.
2. preparation method as described in claim 1, it is characterised in that: during the preparation process, control water in lithium salts use environment
10ppm is respectively less than with oxygen content.
3. preparation method as claimed in claim 1 or 2, it is characterised in that: in step (1), the inorganic molecules are
LiF、LiOH、Li2One or more of S.
4. preparation method as claimed in claim 1 or 2, it is characterised in that: in step (2), the polymeric matrix is poly-
Ethylene oxide, the lithium salts are bis trifluoromethyl sulfimide lithium, lithium perchlorate, di-oxalate lithium borate or bis- (fluorine sulphonyl) Asia
Amine lithium.
5. preparation method as claimed in claim 4, it is characterised in that: the mass ratio of the polyethylene glycol oxide and lithium salts is EO:
Li+=10-20:1.
6. preparation method as claimed in claim 5, it is characterised in that: the mass ratio of the polyethylene glycol oxide and lithium salts is EO:
Li+=15:1.
7. preparation method as claimed in claim 1 or 2, it is characterised in that: the quality dosage of the inorganic molecules is polymerization
The 5-10% of object matrix and lithium salts gross mass.
8. preparation method as claimed in claim 1 or 2, it is characterised in that: in step (2), the time being stirred at room temperature is 24-
48h。
9. preparation method as claimed in claim 1 or 2, it is characterised in that: in step (3), solution is first in room temperature volatilization 2-
12h, then the 12-24h that volatilizees is placed on 50-60 DEG C of warm table.
10. preparation method as claimed in claim 9, it is characterised in that: in step (3), solution first room temperature volatilize 6h, then
The 12h that volatilizees is placed on 50 DEG C of warm tables.
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| CN113206292A (en) * | 2021-04-25 | 2021-08-03 | 华南理工大学 | Polymer-based composite solid electrolyte and preparation method and application thereof |
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Application publication date: 20181218 |