CN109546207A - A kind of composite solid polymer electrolyte film and its preparation method and application - Google Patents
A kind of composite solid polymer electrolyte film and its preparation method and application Download PDFInfo
- Publication number
- CN109546207A CN109546207A CN201811459219.2A CN201811459219A CN109546207A CN 109546207 A CN109546207 A CN 109546207A CN 201811459219 A CN201811459219 A CN 201811459219A CN 109546207 A CN109546207 A CN 109546207A
- Authority
- CN
- China
- Prior art keywords
- composite solid
- polymer electrolyte
- solid polymer
- lithium
- electrolyte film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
- Secondary Cells (AREA)
Abstract
A kind of composite solid polymer electrolyte film and its preparation method and application, dissolves a polymer in organic solvent, stirs evenly after ultrasonic disperse, and lithium salts, nano-ceramic particle, ionic liquid and plasticizer is then added, stirs evenly, and forms slurry；Coating on a glass, forms liquid film；It is dry, obtain composite solid polymer electrolyte film.Composite solid polymer electrolyte film of the invention has high conductivity at room temperature and mechanical strength, preparation process is simple, it can be mass produced, and composite solid polymer electrolyte film of the invention is applied to lithium ion battery with good chemical property.
Description
Technical field
The present invention relates to new type lithium ion battery electrolyte field more particularly to a kind of composite solid polymer electrolyte films
And its preparation method and application.
Background technique
As the increasingly depleted of the non-renewable resources such as petroleum, coal and these energy can generate in use
A degree of environmental pollution.Therefore, a kind of task of clean, green, high-energy density energy storage medium is found
It is extremely urgent.In various cleaning secondary energy sources, lithium ion battery is without suspected of the highest one kind of attention rate.Traditional lithium-ion electric
Pond generally uses the organic solvent for containing lithium salts as electrolyte, although the electrolyte of this form possesses high ionic conductivity
Be conducive to the transmission of lithium ion in battery, but the poor compatibility of lithium metal and liquid electrolyte, in battery charging and discharging circulation
Li dendrite can be generated, protrusion is easily formed and penetrates diaphragm, causes electrolyte to volatilize and reveal, may cause the expansion of battery when serious
It even explodes, becomes the potential major safety risks of lithium ion battery.
For above problem, a series of solid electrolyte is gradually applied in lithium ion battery for substituting liquid
Electrolyte, however, in actual application process, due to the lower influence of solid electrolyte itself ionic conductivity, in room
Application under temperature is restricted, it is also necessary to further research.
Solid electrolyte common at present is divided into, inorganic solid electrolyte and solid polymer electrolyte two major classes.It is inorganic
Solid electrolyte material itself has the performance for meeting lithium ion battery, possesses the room-temperature ion that can be matched in excellence or beauty with liquid electrolyte
Conductivity, but inorganic solid electrolyte bad mechanical strength compare and are difficult into stable film applied in battery, and with
Interface impedance when electrode active material contacts greatly and and electrochemical window it is relatively narrow, therefore there is no large-scale production and application.
Although solid polymer electrolyte possesses stronger processing performance, but the ionic conductivity of its room temperature is low, bad mechanical strength, because
The application environment of this solid polymer electrolyte is very restricted.
In order to solve defect existing for existing solid state electrolyte, nano ceramics is added in solid polymer electrolyte
Grain makes two-way interaction form a kind of novel composite solid electrolyte.As the addition of nano-ceramic particle improves admittedly
The mechanical strength of state polymeric dielectric, and since the addition of nano-ceramic particle reduces the crystallization degree of polymer, have
Conducive to the movement of enhancing polymer segments chain and the migration rate of lithium ion.Also, the collaboration between nano-ceramic particle and lithium salts
Effect, promotes the dissociation of lithium salts, so that the ion concentration between nano-ceramic particle and lithium salts improves.
During carrying out compound with solid polymer electrolyte, nano-ceramic particle is difficult uniformly nano-ceramic particle
Dispersion, current technology fails to provide a kind of more applicable process flow, so not putting into actual production.
Summary of the invention
For the above problems of the prior art, the purpose of the present invention is to provide a kind of composite solid electrostrictive polymers
Plasma membrane and its preparation method and application is solved, preparation process is simple, can be applied to be mass produced, the composite solid polymerization of preparation
Object dielectric film ionic conductivity with higher and preferable mechanical strength, using the composite solid polymer electrolyte film
Lithium ion battery has stable cycle performance and high rate performance.
To achieve the above object, the present invention adopts the following technical scheme that:
A kind of composite solid polymer electrolyte film, including polymer, nano-ceramic particle, lithium salts, ionic liquid and increasing
Mould agent；Wherein, in terms of the gross mass of polymer and nano-ceramic particle, the mass content of nano-ceramic particle is 3%-25%,
In terms of the gross mass of polymer and lithium salts, the mass content of lithium salts is 10%-60%, with the gross mass of polymer and ionic liquid
The mass content of meter, ionic liquid is 1%-40%, and in terms of the gross mass of polymer and plasticizer, the mass content of plasticizer is
1%-10%.
A further improvement of the present invention lies in that in terms of the gross mass of polymer and nano-ceramic particle, nano-ceramic particle
Mass content be 3%-15%, in terms of the gross mass of polymer and lithium salts, the mass content of lithium salts is 10%-30%, with poly-
The gross mass meter of object and ionic liquid is closed, the mass content of ionic liquid is 1%-20%, with total matter of polymer and plasticizer
Meter, the mass content of plasticizer are 1%-5%.
A further improvement of the present invention lies in that in terms of the gross mass of polymer and nano-ceramic particle, nano-ceramic particle
Mass content be 15%-25%, in terms of the gross mass of polymer and lithium salts, the mass content of lithium salts is 30%-60%, with poly-
The gross mass meter of object and ionic liquid is closed, the mass content of ionic liquid is 20%-40%, with total matter of polymer and plasticizer
Meter, the mass content of plasticizer are 5%-10%.
A further improvement of the present invention lies in that the average molecular weight of the polymer is 10-40 ten thousand；The nano ceramics
The mean radius of grain is 5nm-200nm.
A further improvement of the present invention lies in that the polymer is Kynoar, Kynoar-hexafluoropropene, gathers
One of acrylonitrile, polyethylene glycol oxide.
A further improvement of the present invention lies in that the nano-ceramic particle is palygorskite soil, attapulgite, montmorillonite, silicon
One of diatomaceous earth, silica, aluminium oxide, titanium oxide.
A further improvement of the present invention lies in that the lithium salts is bis trifluoromethyl sulfimide lithium, lithium hexafluoro phosphate, tetrafluoro
Lithium borate, lithium perchlorate, dioxalic acid lithium borate, the mixture of any one or more in difluoro lithium sulfimide；It is described
Ionic liquid is glyoxaline ion liquid, quaternary ammonium ionic liquid, piperidines ionic liquid, one in pyrrole ionic liquid
Kind；The plasticizer is ethylene carbonate, polycarbonate, propene carbonate, methyl ethyl carbonate, dimethyl carbonate, O-phthalic
One of diethyl phthalate.
A further improvement of the present invention lies in that glyoxaline ion liquid is two (trimethyl fluoride sulfonyl) 1- ethyl -3- methyl
Imidazoles；Quaternary ammonium ionic liquid is that N- methyl-N, N- diethyl-N- (2- methoxy ethyl) ammonium two (trimethyl fluoride sulfonyl) is sub-
Amine；Piperidines ionic liquid is N- Methyl-N-propyl piperidines two (trimethyl fluoride sulfonyl) imines；Pyrrole ionic liquid is N- first
Base-N- propyl pyrrole two (trimethyl fluoride sulfonyl) imines.
A kind of preparation method of composite solid polymer electrolyte film, comprising the following steps:
S1, it dissolves a polymer in organic solvent, is stirred evenly after ultrasonic disperse, obtain solution；
S2, lithium salts, nano-ceramic particle, ionic liquid and plasticizer are added into solution, stir evenly, form slurry；
S3, slurry is coated on a glass, forms liquid film；
S4, liquid film is dried in vacuo, obtains composite solid polymer electrolyte film.
A further improvement of the present invention lies in that the mass concentration of polymer is 10-30% in solution in step S1；It is organic
Solvent be n,N-Dimethylformamide, n,N-dimethylacetamide, N, N- dimethylpropionamide, N-Methyl pyrrolidone, acetonitrile,
One of acetone；The time of ultrasonic disperse is 10min-40min；The time of stirring is 6-12h；Stirring is at 40 DEG C -65 DEG C
It carries out；
In step S2, the time of stirring is 6-12h；Stirring carries out at 40 DEG C -65 DEG C；
In step S4, vacuum drying temperature is 30-100 DEG C, and the time is 8-24 hours.
A further improvement of the present invention lies in that composite solid polymer electrolyte film thickness is 20 μm -180 μm.
A kind of composite solid polymer electrolyte film is preparing the application in lithium ion battery.
It is above to improve compared with the existing technology, the invention has the benefit that
1. nano ceramics is added in solid polymer electrolyte in order to solve defect existing for existing solid state electrolyte
Grain makes two-way interaction form a kind of novel composite solid electrolyte.As the addition of nano-ceramic particle improves admittedly
The mechanical strength of state polymeric dielectric, and since the addition of nano-ceramic particle reduces the crystallization degree of polymer, have
Conducive to the movement of enhancing polymer segments chain and the migration rate of lithium ion.Synergistic effect between nano-ceramic particle and lithium salts,
The dissociation of lithium salts is promoted, so that the ion concentration between nano-ceramic particle and lithium salts improves.
2. the addition of intermediate ion liquid of the present invention not only improves only the security performance of electrolyte, and also greatly increases
The ionic conductivity of electrolyte accelerates the migration rate of lithium ion in entire battery system, reduces the impedance of battery system.
3. solid electrolyte membrane preparation method provided by the present invention is simple, can be made by simple casting film
It is standby, it can be applied to large-scale production.
4. composite solid electrolyte film prepared by the present invention, can assemble all-solid lithium-ion battery, and have preferable
Cycle performance and high rate performance.
Detailed description of the invention
Fig. 1 is the cycle performance and coulombic efficiency of the solid lithium battery prepared according to the embodiment of the present invention 1.
Fig. 2 is the cycle performance and coulombic efficiency of the solid lithium battery prepared according to the embodiment of the present invention 2.
Fig. 3 is the cycle performance and coulombic efficiency of the solid lithium battery prepared according to the embodiment of the present invention 3.
Specific embodiment
In order to further promote mutual understanding to the present invention, the present invention will now be described in detail with reference to examples.It is listed
For embodiment be in the present invention it is preferred, be only used for carrying out the present invention more complete explanation, but can not be interpreted as pair
The scope of application of the invention is limited.
Composite solid electrolyte film of the invention is illustrated first.
A kind of composite solid polymer electrolyte film is proposed in the present invention, the composite solid polymer electrolyte film
By: polymer, lithium salts, nano-ceramic particle, ionic liquid and plasticizer composition.
Wherein, the polymer is high molecular polymer, and the average molecular weight of high molecular polymer is between 10-40 ten thousand.
The selection of high molecular polymer does not require particularly in the present invention, can be selected according to actual needs.Example
Such as, Kynoar (PVDF), polyacrylonitrile (PAN), Kynoar-hexafluoropropene (PVDF-HFP), polyoxy be can choose
Change one of ethylene (PEO) or a variety of.
Selected nano-ceramic particle can be nanometer grade paligorskite soil, attapulgite, montmorillonite, diatomite, silica
(SiO2), aluminium oxide (Al2O3), titanium oxide (TiO2One of).The mean radius of nano-ceramic particle is in the present invention
5nm-200nm。
Added lithium salts does not require particularly, can select according to actual needs.For example, lithium salts is bis trifluoromethyl
Sulfimide lithium (LITFSI), LIPF6Lithium hexafluoro phosphate (LIPF6)、LIBF4LiBF4 (LIBF4), lithium perchlorate
(LIClO4), dioxalic acid lithium borate (LiBOB), the mixing of any one or more in difluoro lithium sulfimide (LiFSi)
Object.
Selected ionic liquid be glyoxaline ion liquid, quaternary ammonium ionic liquid, piperidines ionic liquid and pyroles from
One of sub- liquid.The ionic conductivity of the dielectric film is improved as a result,.The plasticizer is ethylene carbonate, poly- carbon
One of sour rouge, propene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl phthalate.
Embodiment according to the present invention is preferred, and selected glyoxaline ion liquid is two (trimethyl fluoride sulfonyl) 1- ethyls-
3- methylimidazole；Quaternary ammonium ionic liquid is N- methyl-N, N- diethyl-N- (2- methoxy ethyl) (trifluoromethyl sulphur of ammonium two
Acyl) imines；Piperidines ionic liquid is N- Methyl-N-propyl piperidines two (trimethyl fluoride sulfonyl) imines；Pyrrole ionic liquid
For N- Methyl-N-propyl pyrroles two (trimethyl fluoride sulfonyl) imines.
In terms of the gross mass of polymer and nano-ceramic particle, the mass content of nano-ceramic particle is 3%-25%, with
The mass content of the gross mass meter of polymer and lithium salts, lithium salts is 10%-60%, with the gross mass of polymer and ionic liquid
The mass content of meter, ionic liquid is 1%-40%, and in terms of the gross mass of polymer and plasticizer, the mass content of plasticizer is
1%-10%.
Secondly the preparation process of the composite solid polymer electrolyte film of explanation according to a second aspect of the present invention.
The invention proposes a kind of preparation methods of composite solid electrolyte film, specifically includes the following steps:
S1, it dissolves a polymer in organic solvent, ultrasonic disperse stirs evenly, and obtains mixed solution.Polymer in solution
Concentration be 10-30wt%.The selection of organic solvent does not require particularly, can select according to actual needs.For example, at this
In the embodiment of invention, organic solvent be n,N-Dimethylformamide, n,N-dimethylacetamide, N, N- dimethylpropionamide,
One of N-Methyl pyrrolidone, acetonitrile, acetone.
Ultrasonic disperse is carried out to the solution comprising polymer, sufficiently to dissolve.The time of ultrasonic disperse is not special
It is required that can be adjusted according to actual needs.For example, in an embodiment of the present invention, the ultrasonic disperse time is 10min-
40min.The solution for including polymer is stirred, to be sufficiently mixed.The mode of stirring does not require particularly, Ke Yigen
It is selected according to actual conditions.For example, in an embodiment of the present invention, using mechanical stirring.The time of stirring and temperature do not have
It is special to require, it can be selected according to the actual situation.For example, in an embodiment of the present invention, preferred mixing time is
6-12h；Stirring carries out at 40 DEG C -65 DEG C.
S2, it is added into mixed solution and according to sequencing sequentially adds lithium salts, nano-ceramic particle, ionic liquid and increasing
Agent is moulded, is stirred evenly, slurry is formed.In the gross mass of polymer and lithium salts, the content of lithium salts is 10wt%-60wt%.Polymerization
In the gross mass of object and nano-ceramic particle, the content of nano-ceramic particle is 3wt%-25wt%.Polymer and ionic liquid
Gross mass in, the content of ionic liquid is 1wt%-40wt%, in the gross mass of polymer and plasticizer, the content of plasticizer
For 1wt%-10wt%.In this step, the time of stirring is 6-12h, and stirring carries out at 40 DEG C -65 DEG C.
S3, slurry is coated on a glass by solution casting method, and film thickness is controlled by scraper, form liquid
Film.For example, in an embodiment of the present invention, the mold selected is glass plate.
S4, liquid film is dried in vacuo, removes organic solvent, obtains composite solid polymer electrolyte film.According to this
The embodiment of invention, vacuum drying condition do not specially require, and can be selected according to actual needs.For example, according to this
The embodiment of invention, vacuum drying temperature are 30-100 DEG C, and the vacuum drying time is 8-24 hours.
Illustrate the assembling of all-solid lithium-ion battery according to a third aspect of the present invention again.
The all-solid lithium-ion battery applied according to the present invention includes positive plate, negative electrode tab and is spaced in positive plate and bears
Composite solid polymer electrolyte film between pole piece.Wherein, positive plate include plus plate current-collecting body and be coated on plus plate current-collecting body
On positive active material, positive conductive agent and binder.
In the all-solid lithium-ion battery applied according to the present invention, the plus plate current-collecting body can selected from aluminium foil, copper foil,
Nickel foil, carbon foil, copper foil or stainless steel substrates.
In the all-solid lithium-ion battery applied according to the present invention, the positive active material can be according to actual selection
LiCoO2、LiFePO4Or nickel-cobalt-manganternary ternary anode material.
In the all-solid lithium-ion battery applied according to the present invention, the positive conductive agent can be according to actual selection acetylene
Black, graphite, Super P or conductive fiber.
In the all-solid lithium-ion battery applied according to the present invention, the negative electrode material can be according to actual selection.For example,
Cathode is lithium metal and the negative electrode material based on lithium metal or the negative electrode material based on carbon.
Next the present invention program is described in more details in conjunction with the embodiments.
Embodiment 1
A kind of composite solid electrolyte film, the dielectric film is by Kynoar (PVDF), lithium perchlorate (LIClO4), receive
Rice palygorskite, two (trimethyl fluoride sulfonyl) 1- ethyl-3-methylimidazoles (EMITFSI), dimethyl carbonate (DMC) are made.
The preparation method comprises the following steps: first dispersing PVDF in DMF solvent, in 50 DEG C of magnetic agitation 6h, mixed solution is obtained.?
During this, keeping the mass concentration of PVDF solution is 15%.Then, it is sequentially added into PVDF solution according to sequencing
LIClO4, nanometer palygorskite, EMITFSI and DMC.The LIClO of addition4Account for LIClO4With the 20% of nanometer palygorskite gross mass, add
The nanometer palygorskite entered accounts for the 10wt% of nanometer palygorskite and PVDF gross mass, the quality of the EMITFSI of addition be EMITFSI and
The quality of the 10wt% of PVDF mixture gross mass, the DMC of addition are the 3wt% of DMC and PVDF mixture gross mass, with subsequent
Continuous stirring 12h, sufficiently reaction form slurry.Finally, slurry is cast on smooth glass plate, it is dried in vacuo at 60 DEG C
For 24 hours, composite solid electrolyte film is obtained.
Embodiment 2
A kind of composite solid electrolyte film, the dielectric film is by Kynoar (PVDF), lithium hexafluoro phosphate (LIPF6)、
Nanometer palygorskite, two (trimethyl fluoride sulfonyl) 1- ethyl-3-methylimidazoles (EMITFSI), ethylene carbonate (EC) are made.
The preparation method comprises the following steps: first dispersing PVDF in DMP solvent, in 60 DEG C of magnetic agitation 6h, mixed solution is obtained.?
During this, keeping the mass concentration of PVDF solution is 10%.Then, it is sequentially added into PVDF solution according to sequencing
LIPF6, nanometer palygorskite, EMITFSI and EC.The LIPF of addition6Account for LIPF6With the 20% of nanometer palygorskite gross mass, addition
Nanometer palygorskite accounts for the 15wt% of nanometer palygorskite and PVDF gross mass, and the quality of the EMITFSI of addition is EMITFSI and PVDF
The quality of the 10wt% of mixture gross mass, the EC of addition are the 10wt% of EC and PVDF mixture gross mass, continue thereafter with and stir
12h is mixed, sufficiently reaction forms slurry.Finally, slurry is cast on smooth glass plate, it is dried in vacuo for 24 hours, obtains at 40 DEG C
To composite solid electrolyte film.
Embodiment 3
A kind of composite solid electrolyte film, the dielectric film is by polyethylene glycol oxide (PEO), bis- (trifluoromethyl sulphur) acid imides
Lithium (LITFSI), nano montmorillonite, two (trimethyl fluoride sulfonyl) 1- ethyl-3-methylimidazoles (EMITFSI), ethylene carbonate
(EC) it is made.
The preparation method comprises the following steps: first dispersing PEO in DMF solvent, in 50 DEG C of magnetic agitation 6h, mixed solution is obtained.?
During this, keeping the mass concentration of PEO solution is 15%.Then, it is sequentially added into PEO solution according to sequencing
LITFSI, nano montmorillonite, EMITFSI, EC.The LITFSI of addition accounts for the 10% of LITFSI and nano montmorillonite gross mass, adds
The nano montmorillonite entered accounts for the 15wt% of nano montmorillonite and PEO gross mass, the quality of the EMITFSI of addition be EMITFSI and
The quality of the 20wt% of PEO mixture gross mass, the EC of addition are the 5wt% of EC and PEO mixture gross mass, continue thereafter with and stir
12h is mixed, sufficiently reaction forms slurry.Finally, slurry is cast on smooth glass plate, it is dried in vacuo for 24 hours, obtains at 60 DEG C
To composite solid electrolyte film.
Embodiment 4
A kind of composite solid electrolyte film, the dielectric film by Kynoar (PVDF), lithium perchlorate (LIClO4), receive
Rice silica, two (trimethyl fluoride sulfonyl) 1- ethyl-3-methylimidazoles (EMITFSI), dimethyl carbonate (DMC) are made.
The preparation method comprises the following steps: first dispersing PVDF in DMP solvent, in 60 DEG C of magnetic agitation 6h, mixed solution is obtained.?
During this, keeping the mass concentration of PVDF solution is 10%.Then, it is sequentially added into PVDF solution according to sequencing
LIClO4, nano silicon oxide, EMITFSI, DMC.The LIClO of addition4Account for LIClO4With the 30% of nano silicon oxide gross mass, add
The nano silicon oxide entered accounts for the 10wt% of nano silicon oxide and PVDF gross mass, the quality of the EMITFSI of addition be EMITFSI and
The quality of the 10wt% of PVDF mixture gross mass, the DMC of addition are the 5wt% of DMC and PVDF mixture gross mass, with subsequent
Continuous stirring 12h, sufficiently reaction form slurry.Finally, slurry is cast on smooth glass plate, it is dried in vacuo at 60 DEG C
18h obtains composite solid electrolyte film.
Embodiment 5
PVDF-HFP is dissolved in NMP first, after ultrasonic disperse 10min, obtains mixed solution in 40 DEG C of magnetic agitation 6h.
Wherein, the 15wt% that the mass concentration of PVDF-HFP is.Later, LIClO is sequentially added into mixed solution4, nano aluminium oxide,
N- methyl-N, N- diethyl-N- (2- methoxy ethyl) ammonium two (trimethyl fluoride sulfonyl) imines, EC, the LIClO of addition4It accounts for
LIClO4With the 25% of PVDF-HFP gross mass, the nano aluminium oxide of addition accounts for nano aluminium oxide and PVDF-HFP gross mass
The quality of 5wt%, N- methyl-N, N- diethyl-N- (2- methoxy ethyl) ammonium two (trimethyl fluoride sulfonyl) imines of addition is
N- methyl-N, N- diethyl-N- (2- methoxy ethyl) ammonium two (trimethyl fluoride sulfonyl) imines and PVDF-HFP gross mass
5wt%, the EC of addition account for the 5% of EC and PVDF-HFP gross mass, continue the magnetic agitation 12h at 40 DEG C, are thoroughly mixed to form
Slurry.Finally, slurry is cast on smooth glass plate, it is dried in vacuo at 40 DEG C for 24 hours, obtains composite solid electrolyte
Film.
Embodiment 6
PAN is dissolved in acetonitrile first, after ultrasonic disperse 20min, obtains mixed solution in 60 DEG C of magnetic agitation 6h.Its
In, 10wt% that the mass concentration of PAN is.Later, LiFSi, nano diatomite, N- methyl-are sequentially added into mixed solution
N, N- diethyl-N- (2- methoxy ethyl) ammonium two (trimethyl fluoride sulfonyl) imines and PC, the LiFSi of addition account for LiFSi and PAN
The 25% of gross mass, the nano diatomite of addition account for the 15wt% of nano diatomite and PAN gross mass, the N- methyl-N of addition,
The quality of N- diethyl-N- (2- methoxy ethyl) ammonium two (trimethyl fluoride sulfonyl) imines is N- methyl-N, N- diethyl-N-
The 10wt% of (2- methoxy ethyl) ammonium two (trimethyl fluoride sulfonyl) imines and PAN gross mass, the PC of addition account for the total matter of PC and PAN
The 10% of amount continues the magnetic agitation 12h at 60 DEG C, is thoroughly mixed to form slurry.Finally, slurry to be cast in smooth glass
It on plate, is dried in vacuo at 60 DEG C for 24 hours, obtains composite solid electrolyte film.
Embodiment 7
Prepare all-solid lithium-ion battery
Application of the solid electrolyte membrane prepared by the present invention in solid lithium ion battery, solid state battery use LiFePO4
For anode, the half-cell that lithium metal is cathode, solid electrolyte membrane is applied between positive and negative anodes.
Dielectric film can be the dielectric film in embodiment 1-6.
In the present embodiment, positive LiFePO4 is according to mass ratio LiFePO4: Super P:PVDF=8:1:1 is in NMP
It is mixed to get anode sizing agent, which is coated on aluminium foil, then 110 DEG C of vacuum drying for 24 hours, obtain anode.
In the present embodiment, cathode uses lithium piece, respectively using the electrolyte in embodiment 1, embodiment 2 and embodiment 3
Film assembles button cell in the glove box of argon atmosphere, from being tested.
Referring to figure 1, figure 2 and figure 3, after 100 circulations, the specific capacity of the solid electrolyte membrane be can achieve about
140mAh/g, this, which is primarily due to joined, generates synergistic effect between nanometer palygorskite and lithium salts, promotes the dissociation of lithium salts,
So that the ion concentration between nano-ceramic particle and lithium salts improves.There is certain contribution for ionic conductivity, improves compound
The performance of dielectric film.
Comparative example 1
PVDF is dissolved in DMF solvent, obtains mixed solution in 50 DEG C of magnetic agitation 6h.Wherein the concentration of PVDF solution is
10%, then, LIClO is added into PVDF solution4, wherein the LIClO of addition4Account for LIClO4With the 30% of PVDF gross mass,
It is thoroughly mixed to form slurry.Then, slurry is cast on smooth glass plate, is dried in vacuo at 60 DEG C for 24 hours, obtained compound
Dielectric film.The film-strength is poor, fragile, and after being made into battery, chemical property is poor.
Embodiment 8
A kind of preparation method of composite solid polymer electrolyte film, comprising the following steps:
S1, it dissolves a polymer in organic solvent, stirs 12h at 40 DEG C after ultrasonic disperse 10min, obtain mass concentration
For the solution of 10-30%；
Wherein, organic solvent is n,N-Dimethylformamide；
The polymer is Kynoar.
S2, lithium salts, nano-ceramic particle, ionic liquid and plasticizer are added into solution, 12h, shape is stirred at 40 DEG C
At slurry；Wherein, the mean radius of the nano-ceramic particle is 5nm-200nm, and nano-ceramic particle is palygorskite soil.
The lithium salts is bis trifluoromethyl sulfimide lithium；
The plasticizer is ethylene carbonate.
Ionic liquid is two (trimethyl fluoride sulfonyl) 1- ethyl-3-methylimidazoles；
S3, slurry is coated on a glass by solution casting method, forms liquid film；
S4,30 DEG C of liquid film are dried in vacuo 24 hours, remove organic solvent, obtains 20 μm -180 μm of composite solid
Polymer dielectric film.
Wherein, in terms of the gross mass of polymer and nano-ceramic particle, the mass content of nano-ceramic particle is 25%, with
The gross mass meter of polymer and lithium salts, the mass content of lithium salts are 30%, in terms of the gross mass of polymer and ionic liquid, ion
The mass content of liquid is 1%, and in terms of the gross mass of polymer and plasticizer, the mass content of plasticizer is 1%.
Embodiment 9
A kind of preparation method of composite solid polymer electrolyte film, comprising the following steps:
S1, it dissolves a polymer in organic solvent, stirs 6h at 65 DEG C after ultrasonic disperse 40min, obtain mass concentration
For the solution of 10-30%；
Wherein, organic solvent is N-Methyl pyrrolidone；
The polymer is Kynoar-hexafluoropropene.
S2, lithium salts, nano-ceramic particle, ionic liquid and plasticizer are added into solution, 10h, shape is stirred at 50 DEG C
At slurry；Wherein, the mean radius of the nano-ceramic particle is 5nm-200nm, and nano-ceramic particle is montmorillonite.
The lithium salts is the mixture of lithium hexafluoro phosphate and LiBF4；
The plasticizer is polycarbonate.
Ionic liquid is N- methyl-N, N- diethyl-N- (2- methoxy ethyl) ammonium two (trimethyl fluoride sulfonyl) imines；
S3, slurry is coated on a glass by solution casting method, forms liquid film；
S4,100 DEG C of liquid film are dried in vacuo 8 hours, remove organic solvent, obtains 20 μm -180 μm of composite solid
Polymer dielectric film.
Wherein, in terms of the gross mass of polymer and nano-ceramic particle, the mass content of nano-ceramic particle is 3%, with
The gross mass meter of polymer and lithium salts, the mass content of lithium salts are 10%, in terms of the gross mass of polymer and ionic liquid, ion
The mass content of liquid is 40%, and in terms of the gross mass of polymer and plasticizer, the mass content of plasticizer is 6%.
Embodiment 10
A kind of preparation method of composite solid polymer electrolyte film, comprising the following steps:
S1, it dissolves a polymer in organic solvent, stirs 8h at 55 DEG C after ultrasonic disperse 20min, obtain mass concentration
For the solution of 10-30%；
Wherein, organic solvent is acetonitrile；
The polymer is polyacrylonitrile.
S2, lithium salts, nano-ceramic particle, ionic liquid and plasticizer are added into solution, 6h is stirred at 65 DEG C, formed
Slurry；Wherein, the mean radius of the nano-ceramic particle is 5nm-200nm, and nano-ceramic particle is titanium oxide.
The lithium salts is the mixture of lithium perchlorate, dioxalic acid lithium borate and difluoro lithium sulfimide；
The plasticizer is diethyl phthalate.
Ionic liquid is N- Methyl-N-propyl piperidines two (trimethyl fluoride sulfonyl) imines；
S3, slurry is coated on a glass by solution casting method, forms liquid film；
S4,50 DEG C of liquid film are dried in vacuo 15 hours, remove organic solvent, obtains 20 μm -180 μm of composite solid
Polymer dielectric film.
Wherein, in terms of the gross mass of polymer and nano-ceramic particle, the mass content of nano-ceramic particle is 10%, with
The gross mass meter of polymer and lithium salts, the mass content of lithium salts are 60%, in terms of the gross mass of polymer and ionic liquid, ion
The mass content of liquid is 20%, and in terms of the gross mass of polymer and plasticizer, the mass content of plasticizer is 10%.
In the present invention, nano-ceramic particle is added in solid polymer electrolyte, on the one hand reduces the high scores such as PVDF
The crystallinity of sub- polymer makes polymer segments chain is fully dispersed to open, while ceramic particle will disperse uniformly.It on the other hand is to improve
Film-strength.Two-way interaction is set to form a kind of novel composite solid electrolyte.Between nano-ceramic particle and lithium salts
Synergistic effect, promotes the dissociation of lithium salts, so that the ion concentration between nano-ceramic particle and lithium salts improves.
The addition of intermediate ion liquid of the present invention not only improves only the security performance of electrolyte, and also greatly increases electricity
The ionic conductivity for solving matter, accelerates the migration rate of lithium ion in entire battery system, reduces the impedance of battery system.This
Solid electrolyte membrane preparation method provided in invention is simple, can be prepared, be can be applied to by simple casting film
Large-scale production.
In the present invention, prepared composite solid electrolyte film can assemble all-solid lithium-ion battery, and have preferable
Cycle performance and high rate performance.
Claims (10)
1. a kind of composite solid polymer electrolyte film, which is characterized in that including polymer, nano-ceramic particle, lithium salts, ion
Liquid and plasticizer；Wherein, in terms of the gross mass of polymer and nano-ceramic particle, the mass content of nano-ceramic particle is
3%-25%, in terms of the gross mass of polymer and lithium salts, the mass content of lithium salts is 10%-60%, with polymer and ionic liquid
The mass content of the gross mass meter of body, ionic liquid is 1%-40%, in terms of the gross mass of polymer and plasticizer, plasticizer
Mass content is 1%-10%.
2. a kind of composite solid polymer electrolyte film according to claim 1, which is characterized in that the polymer is put down
Average molecular weight is 10-40 ten thousand；The mean radius of the nano-ceramic particle is 5nm-200nm.
3. a kind of composite solid polymer electrolyte film according to claim 1 or 2, which is characterized in that the polymer
For one of Kynoar, Kynoar-hexafluoropropene, polyacrylonitrile, polyethylene glycol oxide.
4. a kind of composite solid polymer electrolyte film according to claim 1 or 2, which is characterized in that the nanometer pottery
Porcelain particle is one of palygorskite soil, attapulgite, montmorillonite, diatomite, silica, aluminium oxide, titanium oxide.
5. a kind of composite solid polymer electrolyte film according to claim 1, which is characterized in that the lithium salts is double three
Methyl fluoride sulfimide lithium, lithium hexafluoro phosphate, LiBF4, lithium perchlorate, dioxalic acid lithium borate, difluoro lithium sulfimide
In the mixture of any one or more；The ionic liquid is glyoxaline ion liquid, quaternary ammonium ionic liquid, piperidines
One of ionic liquid, pyrrole ionic liquid；The plasticizer is ethylene carbonate, polycarbonate, propene carbonate, carbon
One of sour methyl ethyl ester, dimethyl carbonate, diethyl phthalate.
6. a kind of composite solid polymer electrolyte film according to claim 5, which is characterized in that glyoxaline ion liquid
For two (trimethyl fluoride sulfonyl) 1- ethyl-3-methylimidazoles；Quaternary ammonium ionic liquid is N- methyl-N, N- diethyl-N- (2- first
Oxygroup ethyl) ammonium two (trimethyl fluoride sulfonyl) imines；Piperidines ionic liquid is two (trifluoromethyl of N- Methyl-N-propyl piperidines
Sulphonyl) imines；Pyrrole ionic liquid is N- Methyl-N-propyl pyrroles two (trimethyl fluoride sulfonyl) imines.
7. a kind of preparation method of composite solid polymer electrolyte film described in any one of -6 according to claim 1,
It is characterized in that, comprising the following steps:
S1, it dissolves a polymer in organic solvent, is stirred evenly after ultrasonic disperse, obtain solution；
S2, lithium salts, nano-ceramic particle, ionic liquid and plasticizer are added into solution, stir evenly, form slurry；
S3, slurry is coated on a glass, forms liquid film；
S4, liquid film is dried in vacuo, obtains composite solid polymer electrolyte film.
8. a kind of preparation method of composite solid polymer electrolyte film according to claim 7, which is characterized in that
In step S1, the mass concentration of polymer is 10-30% in solution；Organic solvent is n,N-Dimethylformamide, N, N-
Dimethyl acetamide, N, one of N- dimethylpropionamide, N-Methyl pyrrolidone, acetonitrile, acetone；The time of ultrasonic disperse
For 10min-40min；The time of stirring is 6-12h；Stirring carries out at 40 DEG C -65 DEG C；
In step S2, the time of stirring is 6-12h；Stirring carries out at 40 DEG C -65 DEG C；
In step S4, vacuum drying temperature is 30-100 DEG C, and the time is 8-24 hours.
9. a kind of preparation method of composite solid polymer electrolyte film according to claim 7, which is characterized in that compound
Solid polymer electrolyte membrane is with a thickness of 20 μm -180 μm.
10. a kind of composite solid polymer electrolyte film described in any one of -6 according to claim 1 is preparing lithium ion
Application in battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811459219.2A CN109546207A (en) | 2018-11-30 | 2018-11-30 | A kind of composite solid polymer electrolyte film and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811459219.2A CN109546207A (en) | 2018-11-30 | 2018-11-30 | A kind of composite solid polymer electrolyte film and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109546207A true CN109546207A (en) | 2019-03-29 |
Family
ID=65851642
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811459219.2A Pending CN109546207A (en) | 2018-11-30 | 2018-11-30 | A kind of composite solid polymer electrolyte film and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109546207A (en) |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109888382A (en) * | 2019-04-15 | 2019-06-14 | 哈尔滨理工大学 | A kind of preparation method of clay enhancing solid polyelectrolyte film |
| CN110165295A (en) * | 2019-06-03 | 2019-08-23 | 宁德新能源科技有限公司 | Composite electrolyte and the electrochemical appliance and electronic device for using it |
| CN110265719A (en) * | 2019-06-04 | 2019-09-20 | 江西力能新能源科技有限公司 | A kind of electrolyte and its preparation process of lithium battery |
| CN110600664A (en) * | 2019-10-25 | 2019-12-20 | 苏州清陶新能源科技有限公司 | Battery diaphragm, preparation method thereof and battery comprising battery diaphragm |
| CN110828906A (en) * | 2019-11-22 | 2020-02-21 | 四川贝克特瑞科技有限公司 | Preparation method and application of polymer-based solid electrolyte |
| CN111106391A (en) * | 2019-12-11 | 2020-05-05 | 西安交通大学 | Preparation method and application of high-strength solid electrolyte membrane |
| CN111540948A (en) * | 2020-05-09 | 2020-08-14 | 中国乐凯集团有限公司 | Composite solid polymer electrolyte membrane and preparation method and application thereof |
| CN111682259A (en) * | 2020-05-06 | 2020-09-18 | 华南理工大学 | Polymer electrolyte based on ionic liquid and preparation method and application thereof |
| CN111755736A (en) * | 2019-03-26 | 2020-10-09 | 广州大学 | Lithium battery solid electrolyte based on zirconium-based pillared clay and preparation method and application thereof |
| CN111900468A (en) * | 2020-08-11 | 2020-11-06 | 珠海冠宇电池股份有限公司 | Solid electrolyte, preparation method thereof and lithium ion battery |
| CN112787040A (en) * | 2019-10-22 | 2021-05-11 | 辉能科技股份有限公司 | Ceramic barrier layer |
| CN112812635A (en) * | 2020-12-31 | 2021-05-18 | 江苏极信环保科技有限公司 | Negative oxygen ion interior wall decorative coating and preparation method thereof |
| CN112993380A (en) * | 2021-02-04 | 2021-06-18 | 东莞市创明电池技术有限公司 | Organic solid electrolyte and application thereof |
| CN113054238A (en) * | 2019-12-29 | 2021-06-29 | 江西格林德能源有限公司 | Composite solid electrolyte and preparation method thereof |
| FR3110776A1 (en) * | 2020-05-20 | 2021-11-26 | Saft | GELIFIED ELECTROLYTE FOR LITHIUM ELECTROCHEMICAL ELEMENT |
| CN113745648A (en) * | 2020-05-27 | 2021-12-03 | 中石化南京化工研究院有限公司 | Electrochemical energy storage polymer electrolyte and preparation method thereof |
| CN113782741A (en) * | 2020-06-09 | 2021-12-10 | 丰田自动车株式会社 | Binder composition, method for producing binder composition, and method for producing all-solid-state battery |
| CN113937362A (en) * | 2021-09-24 | 2022-01-14 | 中化学南方建设投资有限公司 | Safe and efficient polymer electrolyte lithium battery and preparation method thereof |
| CN114006034A (en) * | 2021-10-29 | 2022-02-01 | 重庆交通大学绿色航空技术研究院 | Three-dimensional glass fiber cloth-based solid electrolyte and preparation method and application thereof |
| CN114335701A (en) * | 2022-02-23 | 2022-04-12 | 贵州梅岭电源有限公司 | Composite solid electrolyte membrane and preparation method thereof |
| CN114373995A (en) * | 2021-12-20 | 2022-04-19 | 河北金力新能源科技股份有限公司 | Composite solid polymer electrolyte and preparation method thereof |
| CN114388878A (en) * | 2020-10-19 | 2022-04-22 | 江西省钒电新能源有限公司 | Composite solid electrolyte and preparation method and application thereof |
| CN114497683A (en) * | 2021-12-28 | 2022-05-13 | 广东微电新能源有限公司 | Composite solid electrolyte and preparation method thereof |
| WO2024083012A1 (en) * | 2022-10-20 | 2024-04-25 | 张家港市国泰华荣化工新材料有限公司 | Lithium ion electrolytic solution, gel polymer electrolyte, and lithium ion battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104466243A (en) * | 2014-12-09 | 2015-03-25 | 上海交通大学 | Composite all-solid-state polymer electrolyte and preparation method thereof |
| CN107039680A (en) * | 2016-02-03 | 2017-08-11 | 三星电子株式会社 | Solid electrolyte and the lithium battery for including the solid electrolyte |
| CN108539260A (en) * | 2018-04-13 | 2018-09-14 | 中国航发北京航空材料研究院 | With multiple Li+Compound organic solid electrolyte of conduction path and preparation method thereof |
-
2018
- 2018-11-30 CN CN201811459219.2A patent/CN109546207A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104466243A (en) * | 2014-12-09 | 2015-03-25 | 上海交通大学 | Composite all-solid-state polymer electrolyte and preparation method thereof |
| CN107039680A (en) * | 2016-02-03 | 2017-08-11 | 三星电子株式会社 | Solid electrolyte and the lithium battery for including the solid electrolyte |
| CN108539260A (en) * | 2018-04-13 | 2018-09-14 | 中国航发北京航空材料研究院 | With multiple Li+Compound organic solid electrolyte of conduction path and preparation method thereof |
Cited By (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111755736A (en) * | 2019-03-26 | 2020-10-09 | 广州大学 | Lithium battery solid electrolyte based on zirconium-based pillared clay and preparation method and application thereof |
| CN109888382A (en) * | 2019-04-15 | 2019-06-14 | 哈尔滨理工大学 | A kind of preparation method of clay enhancing solid polyelectrolyte film |
| CN110165295A (en) * | 2019-06-03 | 2019-08-23 | 宁德新能源科技有限公司 | Composite electrolyte and the electrochemical appliance and electronic device for using it |
| CN110165295B (en) * | 2019-06-03 | 2021-01-19 | 宁德新能源科技有限公司 | Composite electrolyte, and electrochemical device and electronic device using same |
| CN110265719A (en) * | 2019-06-04 | 2019-09-20 | 江西力能新能源科技有限公司 | A kind of electrolyte and its preparation process of lithium battery |
| CN112787040A (en) * | 2019-10-22 | 2021-05-11 | 辉能科技股份有限公司 | Ceramic barrier layer |
| CN112787040B (en) * | 2019-10-22 | 2023-03-24 | 辉能科技股份有限公司 | Ceramic barrier layer |
| CN110600664A (en) * | 2019-10-25 | 2019-12-20 | 苏州清陶新能源科技有限公司 | Battery diaphragm, preparation method thereof and battery comprising battery diaphragm |
| CN110600664B (en) * | 2019-10-25 | 2022-11-11 | 苏州清陶新能源科技有限公司 | Battery diaphragm, preparation method thereof and battery comprising battery diaphragm |
| CN110828906A (en) * | 2019-11-22 | 2020-02-21 | 四川贝克特瑞科技有限公司 | Preparation method and application of polymer-based solid electrolyte |
| CN111106391A (en) * | 2019-12-11 | 2020-05-05 | 西安交通大学 | Preparation method and application of high-strength solid electrolyte membrane |
| CN113054238A (en) * | 2019-12-29 | 2021-06-29 | 江西格林德能源有限公司 | Composite solid electrolyte and preparation method thereof |
| CN113054238B (en) * | 2019-12-29 | 2022-10-28 | 江西格林德能源有限公司 | Composite solid electrolyte and preparation method thereof |
| CN111682259A (en) * | 2020-05-06 | 2020-09-18 | 华南理工大学 | Polymer electrolyte based on ionic liquid and preparation method and application thereof |
| CN111540948A (en) * | 2020-05-09 | 2020-08-14 | 中国乐凯集团有限公司 | Composite solid polymer electrolyte membrane and preparation method and application thereof |
| FR3110776A1 (en) * | 2020-05-20 | 2021-11-26 | Saft | GELIFIED ELECTROLYTE FOR LITHIUM ELECTROCHEMICAL ELEMENT |
| CN113745648A (en) * | 2020-05-27 | 2021-12-03 | 中石化南京化工研究院有限公司 | Electrochemical energy storage polymer electrolyte and preparation method thereof |
| CN113782741A (en) * | 2020-06-09 | 2021-12-10 | 丰田自动车株式会社 | Binder composition, method for producing binder composition, and method for producing all-solid-state battery |
| US11912853B2 (en) | 2020-06-09 | 2024-02-27 | Toyota Jidosha Kabushiki Kaisha | Binder composition, method of producing binder composition, and method of producing all-solid-state battery |
| CN111900468B (en) * | 2020-08-11 | 2022-08-30 | 珠海冠宇电池股份有限公司 | Solid electrolyte, preparation method thereof and lithium ion battery |
| CN111900468A (en) * | 2020-08-11 | 2020-11-06 | 珠海冠宇电池股份有限公司 | Solid electrolyte, preparation method thereof and lithium ion battery |
| CN114388878A (en) * | 2020-10-19 | 2022-04-22 | 江西省钒电新能源有限公司 | Composite solid electrolyte and preparation method and application thereof |
| CN114388878B (en) * | 2020-10-19 | 2023-11-03 | 江西省钒电新能源有限公司 | Composite solid electrolyte and preparation method and application thereof |
| CN112812635A (en) * | 2020-12-31 | 2021-05-18 | 江苏极信环保科技有限公司 | Negative oxygen ion interior wall decorative coating and preparation method thereof |
| CN112993380A (en) * | 2021-02-04 | 2021-06-18 | 东莞市创明电池技术有限公司 | Organic solid electrolyte and application thereof |
| CN113937362A (en) * | 2021-09-24 | 2022-01-14 | 中化学南方建设投资有限公司 | Safe and efficient polymer electrolyte lithium battery and preparation method thereof |
| CN114006034A (en) * | 2021-10-29 | 2022-02-01 | 重庆交通大学绿色航空技术研究院 | Three-dimensional glass fiber cloth-based solid electrolyte and preparation method and application thereof |
| CN114373995A (en) * | 2021-12-20 | 2022-04-19 | 河北金力新能源科技股份有限公司 | Composite solid polymer electrolyte and preparation method thereof |
| CN114497683A (en) * | 2021-12-28 | 2022-05-13 | 广东微电新能源有限公司 | Composite solid electrolyte and preparation method thereof |
| CN114335701A (en) * | 2022-02-23 | 2022-04-12 | 贵州梅岭电源有限公司 | Composite solid electrolyte membrane and preparation method thereof |
| WO2024083012A1 (en) * | 2022-10-20 | 2024-04-25 | 张家港市国泰华荣化工新材料有限公司 | Lithium ion electrolytic solution, gel polymer electrolyte, and lithium ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109546207A (en) | A kind of composite solid polymer electrolyte film and its preparation method and application | |
| CN110581314B (en) | Multilayer-structure composite solid electrolyte membrane, preparation method thereof and solid battery | |
| CN109065945A (en) | A kind of solid electrolyte membrane and its preparation method and application | |
| CN111106391A (en) | Preparation method and application of high-strength solid electrolyte membrane | |
| CN107275671A (en) | A kind of electrolyte and preparation method and lithium battery for suppressing Li dendrite | |
| CN110707287B (en) | Metal lithium negative electrode, preparation method thereof and lithium battery | |
| CN112018430A (en) | Composite solid electrolyte prepared based on in-situ thermal polymerization method and preparation method and application thereof | |
| CN111403658A (en) | Preparation method of diaphragm with electrocatalysis function and application of diaphragm in lithium-sulfur battery | |
| CN110534795A (en) | The preparation method and solid state battery of solid state battery | |
| CN106876633A (en) | A kind of composite diaphragm, lithium battery and preparation method thereof | |
| CN111697262A (en) | Composite solid electrolyte, all-solid-state lithium ion battery and preparation method thereof | |
| CN109904514A (en) | Two-layer compound solid electrolyte and its preparation method and application | |
| CN105870449B (en) | A kind of all solid state lithium-air battery composite positive pole and all solid state lithium-air battery | |
| Jiang et al. | Surface modification and structure constructing for improving the lithium ion transport properties of PVDF based solid electrolytes | |
| CN111952672A (en) | Preparation method and application of high-performance solid electrolyte composite membrane | |
| JP2016532275A (en) | Additives for improving ionic conductivity of lithium ion battery electrodes | |
| CN114335536B (en) | Plastic crystal modified positive electrode solid-state battery and preparation method thereof | |
| CN113421995B (en) | Gel-state electrode and preparation method thereof | |
| CN109818055A (en) | A kind of electrolyte of the anti-thermal runaway of width warm area and its serondary lithium battery of composition | |
| CN108615941A (en) | A kind of additive of anti-thermal runaway and its application in secondary lithium metal | |
| CN109167063A (en) | A kind of lithium anode and its preparation method and application of artificial solid electrolyte interface layer protection | |
| CN113506914A (en) | Ternary lithium ion battery electrolyte and lithium ion battery containing same | |
| CN113346129A (en) | Composite solid electrolyte and preparation method and application thereof | |
| Ren et al. | Hydroxypropylmethylcellulose: Functional material carrier for in-situ solid electrolyte engineering of advanced lithium metal batteries | |
| CN114335700A (en) | Solid electrolyte membrane and preparation method thereof, secondary battery and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190329 |