CN110518279A - A kind of composite solid electrolyte and preparation method thereof of PEO cladding activation nano particle - Google Patents
A kind of composite solid electrolyte and preparation method thereof of PEO cladding activation nano particle Download PDFInfo
- Publication number
- CN110518279A CN110518279A CN201910857634.1A CN201910857634A CN110518279A CN 110518279 A CN110518279 A CN 110518279A CN 201910857634 A CN201910857634 A CN 201910857634A CN 110518279 A CN110518279 A CN 110518279A
- Authority
- CN
- China
- Prior art keywords
- nano particle
- composite solid
- activation
- peo
- solid electrolyte
- 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.)
- Granted
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
- H01M10/052—Li-accumulators
-
- 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
-
- 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
- H01M2300/0088—Composites
- H01M2300/0094—Composites in the form of layered products, e.g. coatings
-
- 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
The invention discloses the composite solid electrolyte and preparation method thereof that a kind of PEO coats activation nano particle, composite solid electrolyte is made of mass percent 60-90% activation nano particle, 10-40% polymer；Further, activation nano particle is then made of the liquid electrolyte for accounting for composite solid electrolyte gross mass percentage 20-40% nano particle and 30-50%.Composite solid electrolyte room-temperature conductivity prepared by the present invention reaches as high as 10‑3Scm‑1, have the characteristics that inorganic matter rigidity and polymer flexibility；The electrolyte is applied in lithium ion solid state battery system, reduces interface impedance, maintains good conductivity, and the cycle performance of lithium battery is efficient, and capacity is stablized.
Description
Technical field
The present invention relates to the technical fields of lithium metal battery more particularly to a kind of PEO cladding to activate the compound of nano particle
Solid electrolyte and preparation method thereof.
Background technique
Currently, coming into being to solve safety problems, the solid electrolytes such as the inflammable, leakiness of electrolyte in battery.Wherein
There is orderly duct, multi-functional structure, excellent thermostabilization by the solid electrolyte of matrix of materials such as ZIF, MOF, COF
Property, approach can be provided for the directional transmissions of ion.The research direction new as the development of solid electrolyte.If but directly with more
Porous materials ZIF, MOF, COF are that carrier is pressed into solid electrolyte, are existed and the solid-state of inorganic oxide or sulfide substrate electricity
The similar interfacial contact problem of matter is solved, and the electrolyte being made into is without flexibility, to influence its application in battery system.
Generally have the characteristics that preferable interfacial contact and flexibility using the solid electrolyte that polymer P EO is coated, still
Since such solid polyelectrolyte room-temperature conductivity is lower, its application is thus defined.Using active porous material as matrix,
On its surface, cladding a thin layer PEO polymer forms composite solid electrolyte film, and PEO can not only make in composite solid electrolyte film
For the medium of ion transmission, cementation can also be played.The characteristic that there is the composite solid electrolyte " rigid ", " soft " to combine,
Improve the interface contact performance of positive and negative anodes and composite solid electrolyte.
Summary of the invention
It is an object of the invention to for the problems in above-mentioned background technology, provide a kind of PEO cladding activation nano particle
Composite solid electrolyte and preparation method thereof.
To achieve the above object, the present invention provides a kind of composite solid electrolyte of PEO cladding activation nano particle, special
Sign is that composite solid electrolyte is made of mass percent 60-90% activation nano particle, 10-40% polymer P EO；Its
Middle activation nano particle is then by accounting for the liquid of composite solid electrolyte gross mass percentage 20-40% nano particle and 30-50%
Electrolyte is constituted.
Further, the nano particle is that the caged porous nanometer material with topological structure is constituted；
Preferably, the material of the nano particle is one of ZIF, MOF, COF, molecular sieve or a variety of.
Further, the liquid electrolyte is made of alkali metal salt and solvent；
Preferably, the alkali metal salt is LiPF6、LiAsF6、LiBF4、LiClO4、LiN(SO2CF3)2、LiCF3SO3In
It is one or more；
Optional, the solvent is one of EC, DMC, EMC, FEC, TEGDME, DME, VC, DMSO, PC, PEG, DOL
Or it is a variety of.
The preparation method for activating the composite solid electrolyte of nano particle is coated the present invention also provides a kind of PEO,
It is characterized in that,
It activates the acquisition of nano particle: being dissolved in alkali metal salt vacuum drying nano particle in glove box organic molten
The liquid electrolyte that agent obtains is mixed according to the ratio of 20-50g/L, and stirring makes liquid electrolyte well into nanoporous
In the duct of material, rear centrifugation, washing, room temperature in vacuo is dry under inert gas shielding atmosphere again, until become powder state,
The wherein 10-30wt.% of totality powder quality shared by liquid electrolyte, after ground in glove box；It is preferred that grinding 10-30min,
Obtain activation nano particle；
The acquisition of the composite solid electrolyte film of PEO cladding activation nano particle: polymer P EO and resulting activation are received
Grinding keeps PEO fully dispersed into activation nano particle after rice grain mixing；It is preferred that grinding 10-20min；Use liquid at room temperature afterwards
Press compacting.
Further, in the acquisition step of the activation nano particle, contain alkali metal salt soln in the liquid electrolyte
Concentration be 0.5-2mol/L.
Further, in the acquisition step of the activation nano particle, moisture in the vacuum drying nano-porous materials
Content is less than 0.1%；Preferably, by nano-porous materials, drying makes moisture content in nano-porous materials at 60-150 DEG C
Less than 0.1%.
Further, in the acquisition step of the activation nano particle, the inert gas under the inert gas shielding atmosphere
For high-purity Ar atmosphere；
Optional, the room temperature under the inert gas shielding atmosphere in room temperature in vacuo drying is 20-40 DEG C.
Further, described hydraulic in the acquisition step of the composite solid electrolyte film of the PEO cladding activation nano particle
The pressure that machine compacting uses is 3-15MPa.
Further, in the acquisition step of the composite solid electrolyte film of the PEO cladding activation nano particle, the compacting
With a thickness of 40-220 μm.
The term and its abbreviation involved in the present invention arrived are as follows: ethylene carbonate (EC), dimethyl carbonate (DMC), ethyl
Methyl carbonic (EMC), fluorinated ethylene carbonate (FEC), tetraethyleneglycol dimethyl ether (TEGDME), glycol dimethyl ether (DME),
Vinylene carbonate (VC), dimethyl sulfoxide (DMSO), propene carbonate (PC), polyethylene glycol (PEG), 1,3- dioxolanes
(DOL)。
The technical solution has technical effect beneficial below:
The composite solid electrolyte of PEO cladding activation nano particle prepared by the present invention not only has polymer dielectric flexible
The advantages of, and having the skeleton rigid structure of inorganic porous material, the nano particle matrix coupled hardness with softness, while used has one
Intensity and thermal stability are determined, so that the safety of composite electrolyte membrane is greatly improved.Gained activates nanometer after activated
Grain, shows the compatibility more excellent with polymer, can inhibit the crystallinity of polymer, improve the ion transporting of polymer
Can, improve the conductivity of composite solid electrolyte.In lithium battery applications, have between composite solid electrolyte film and anode, cathode
Preferable interfacial contact, reduces interface impedance, maintains good conductivity, the cycle performance of lithium battery is efficient, and capacity is steady
It is fixed.
Detailed description of the invention
Fig. 1 be in example 1 the composite solid electrolyte film for preparing in LiFePO4 (LFP) system, room temperature 0.1C multiplying power item
Charge and discharge electrical schematic under part.
Fig. 2 be in example 1 the composite solid electrolyte film for preparing in LiFePO4 (LFP) system, room temperature 0.1C multiplying power item
Cycle performance schematic diagram under part.
Specific embodiment
The embodiment of the present invention is described below in detail, examples of the embodiments are shown in the accompanying drawings, wherein from beginning to end
Same or similar label indicates same or similar element or element with the same or similar functions.Below with reference to attached
The embodiment of figure description is exemplary, it is intended to is used to explain the present invention, and is not considered as limiting the invention.Embodiment
In particular technique or condition person is not specified, described technology or conditions or according to the description of product according to the literature in the art
Book carries out.Reagents or instruments used without specified manufacturer, being can be with conventional products that are commercially available.
A kind of composite solid electrolyte of PEO cladding activation nano particle, which is characterized in that composite solid electrolyte is by matter
Measure percentage 60-90% activation nano particle, 10-40% polymer P EO is constituted；Wherein activation nano particle is then by accounting for composite solid
The liquid electrolyte of state electrolyte gross mass percentage 20-40% nano particle and 30-50% are constituted.
Further, the nano particle is that the caged porous nanometer material with topological structure is constituted；
Preferably, the material of the nano particle is one of ZIF, MOF, COF, molecular sieve or a variety of.
Further, the liquid electrolyte is made of alkali metal salt and solvent；
Preferably, the alkali metal salt is LiPF6、LiAsF6、LiBF4、LiClO4、LiN(SO2CF3)2、LiCF3SO3In
It is one or more；
Optional, the solvent is one of EC, DMC, EMC, FEC, TEGDME, DME, VC, DMSO, PC, PEG, DOL
Or it is a variety of.
A kind of preparation method of the composite solid electrolyte of the PEO cladding activation nano particle, which is characterized in that
It activates the acquisition of nano particle: being dissolved in alkali metal salt vacuum drying nano particle in glove box organic molten
The liquid electrolyte that agent obtains is mixed according to the ratio of 20-50g/L, and stirring makes liquid electrolyte well into nanoporous
In the duct of material, rear centrifugation, washing, room temperature in vacuo is dry under inert gas shielding atmosphere again, until become powder state,
The wherein 10-30wt.% of totality powder quality shared by liquid electrolyte, after ground in glove box；It is preferred that grinding 10-30min,
Obtain activation nano particle；
The acquisition of the composite solid electrolyte film of PEO cladding activation nano particle: polymer P EO and resulting activation are received
Grinding keeps PEO fully dispersed into activation nano particle after rice grain mixing；It is preferred that grinding 10-20min；Use liquid at room temperature afterwards
Press compacting.
Further, in the acquisition step of the activation nano particle, contain alkali metal salt soln in the liquid electrolyte
Concentration be 0.5-2mol/L.
Further, in the acquisition step of the activation nano particle, moisture in the vacuum drying nano-porous materials
Content is less than 0.1%；Preferably, by nano-porous materials, drying makes moisture content in nano-porous materials at 60-150 DEG C
Less than 0.1%.
Further, in the acquisition step of the activation nano particle, the inert gas under the inert gas shielding atmosphere
For high-purity Ar atmosphere；
Optional, the room temperature under the inert gas shielding atmosphere in room temperature in vacuo drying is 20-40 DEG C.
Further, described hydraulic in the acquisition step of the composite solid electrolyte film of the PEO cladding activation nano particle
The pressure that machine compacting uses is 3-15MPa.
Further, in the acquisition step of the composite solid electrolyte film of the PEO cladding activation nano particle, the compacting
With a thickness of 40-220 μm.
Embodiment 1:
A kind of composite solid electrolyte film that the activation nano particle by PEO cladding is prepared, the composite solid electricity
Solving and activating nano particle in nano particle in plasma membrane is ZIF-8, and liquid electrolyte is lithium electrolytic secondary (1M LiPF6,EC:
DMC:EMC=1:1:1), the mass ratio of activation ZIF-8 nano particle and polymer P EO are 75:25；Activate nano particle ZIF-8
The mass ratio of middle nano particle ZIF-8 and liquid electrolyte is 35:40.
Activate the acquisition of nano particle:
(1) preparation of ZIF-8 nano particle
Take powder Zn (NO3)2·6H21.4875g, 1.6421g are placed in conical flask respectively for O and 2-methylimidazole, then
100mL methanol solution is added, stirs 3min, is then stored at room temperature for 24 hours；Remove supernatant, with methanol centrifugation, washs dry sample
Product are then placed in baking oven at 80 DEG C and toast 3 days, grind afterwards spare.
(2) preparation of ZIF-8 nano particle is activated
Above-mentioned ZIF-8 nano particle is placed at 60 DEG C of vacuum oven 3 days dry.In glove box, after taking drying
ZIF-8 powder granule 200mg be placed in 10mL vial, then be added 6mL electrolyte (1M LiPF6,EC:DMC:EMC
=1:1:1), it is stirred 2 days in glove box, removes supernatant, with DMC centrifuge washing, and the room in the case where inertia protects gas Ar atmosphere
Temperature vacuum drying 12h, gained powder granule is ground in glove box, fully dispersed, final to obtain activation ZIF-8 nanometers
Grain.
The acquisition of the composite solid electrolyte film of PEO cladding activation nano particle:
Powder polymer P EO is weighed respectively and activation ZIF-8 nano particle 25mg, 75mg are placed in mortar, is ground
5min.Room temperature suppresses 10min under 7MPa pressure afterwards, forms the composite solid electrolyte film with PEO cladding ZIF-8.
The present embodiment prepares the composite solid electrolyte film room-temperature conductivity of PEO cladding activation ZIF-8 nano particle up to 10- 3Scm-1, by the test in terms of composite solid electrolyte film progress electrochemistry.From figure 1 it appears that prepared in the present embodiment
The activation ZIF-8 nano-particles reinforcement solid electrolyte membrane of PEO cladding is in LFP system in application, in room temperature 0.1C multiplying power item
Under part, preceding 20 circle charging and discharging curve is essentially coincided, and charge and discharge platform current potential is respectively as follows: 3.47V and 3.4V.
Fig. 2 be the composite membrane of this example preparation in LFP system in application, cycle performance curve under the conditions of room temperature 0.1C.
Battery capacity is played in 150mAh/g in LFP system it can be seen from Fig. 2 test result, and capacity is not substantially after 40 circle circulations
It changes, and the efficiency of battery system is close to 100%.
Embodiment 2:
Unlike the first embodiment, activation nano particle is different from the mass ratio of liquid electrolyte, thus structure for the present embodiment
At a kind of composite solid electrolyte, the quality of ZIF-8 nano particle and polymer P EO is activated in the composite solid electrolyte film
Than for 60:40；Activating the mass ratio of nano particle ZIF-8 and liquid electrolyte in nano particle ZIF-8 is 35:40.
Activate the acquisition of nano particle:
(1) preparation of ZIF-8 nano particle
Take powder Zn (NO3)2·6H21.4875g, 1.6421g are placed in conical flask respectively for O and 2-methylimidazole, then
100mL methanol solution is added, stirs 3min, is then stored at room temperature for 24 hours；Remove supernatant, with methanol centrifugation, washs dry sample
Product are then placed in baking oven at 80 DEG C and toast 3 days, grind afterwards spare.
(2) preparation of ZIF-8 nano particle is activated
Above-mentioned ZIF-8 nano particle is placed at 60 DEG C of vacuum oven 3 days dry.In glove box, after taking drying
ZIF-8 powder granule 200mg be placed in 10mL vial, then be added 6mL electrolyte (1M LiPF6,EC:DMC:EMC
=1:1:1), it is stirred 2 days in glove box, removes supernatant, with DMC centrifuge washing, and the room in the case where inertia protects gas Ar atmosphere
Temperature vacuum drying 12h, gained powder granule is ground in glove box, fully dispersed, final to obtain activation ZIF-8 nanometers
Grain.
The acquisition of the composite solid electrolyte film of PEO cladding activation nano particle:
Powder polymer P EO is weighed respectively and activation ZIF-8 nano particle 40mg, 60mg are placed in mortar, is ground
10min.Room temperature suppresses 10min under 3-5MPa pressure afterwards, forms the composite solid electrolyte film with PEO cladding ZIF-8.This
Embodiment prepares the composite solid electrolyte film room-temperature conductivity of PEO cladding activation ZIF-8 nano particle up to 10-5Scm-1。
Embodiment 3:
Unlike the first embodiment, activation nano particle is different from the mass ratio of liquid electrolyte, thus structure for the present embodiment
At a kind of composite solid electrolyte, the quality of ZIF-8 nano particle and polymer P EO is activated in the composite solid electrolyte film
Than for 90:10；Activating the mass ratio of nano particle ZIF-8 and liquid electrolyte in nano particle ZIF-8 is 35:40.
Activate the acquisition of nano particle:
(1) preparation of ZIF-8 nano particle
Take powder Zn (NO3)2·6H21.4875g, 1.6421g are placed in conical flask respectively for O and 2-methylimidazole, then
100mL methanol solution is added, stirs 3min, is then stored at room temperature for 24 hours；Remove supernatant, with methanol centrifugation, washs dry sample
Product are then placed in baking oven at 80 DEG C and toast 3 days, grind afterwards spare.
(2) preparation of ZIF-8 nano particle is activated
Above-mentioned ZIF-8 nano particle is placed at 60 DEG C of vacuum oven 3 days dry.In glove box, after taking drying
ZIF-8 powder granule 200mg be placed in 10mL vial, then be added 6mL electrolyte (1M LiPF6,EC:DMC:EMC
=1:1:1), it is stirred 2 days in glove box, removes supernatant, with DMC centrifuge washing, and the room in the case where inertia protects gas Ar atmosphere
Temperature vacuum drying 12h, gained powder granule is ground in glove box, fully dispersed, final to obtain activation ZIF-8 nanometers
Grain.
The acquisition of the composite solid electrolyte film of PEO cladding activation nano particle:
Powder polymer P EO is weighed respectively and activation ZIF-8 nano particle 10mg, 90mg are placed in mortar, is ground
5min.Room temperature suppresses 20min under 8-9MPa pressure afterwards, forms the composite solid electrolyte film with PEO cladding ZIF-8.
The present embodiment prepares the composite solid electrolyte film room-temperature conductivity of PEO cladding activation ZIF-8 nano particle up to 10- 5Scm-1。
Embodiment 4:
A kind of composite solid electrolyte film that the activation nano particle by PEO cladding is prepared, the composite solid electricity
Solving and activating nano particle in nano particle in plasma membrane is M-TpBD (COF), and liquid electrolyte is lithium electrolytic secondary (1M
LiPF6, EC:DMC:EMC=1:1:1), the mass ratio of activation M-TpBD nano particle and polymer P EO are 75:25；Wherein receive
Rice grain M-ToBD and liquid electrolyte mass ratio are 20:55.
Activate the acquisition of nano particle:
(1) M-TpBD nano particle synthesizes
Take 1.66g benzidine (BD), 10g p-methyl benzenesulfonic acid (PTSA), 5mL water in 25mL conical flask, stirring 5min is mixed
It closes uniform；1.26g1,3,5- TRIMETHYL PHLOROGLUCINOL (Tp) is added afterwards and stirs 5min.In 105 DEG C of temperature after 90 DEG C of bakings for 24 hours
Under continue baking for 24 hours, grind later spare.
(2) preparation of M-TpBD material is activated
In glove box, the M-TpBD powder granule 300mg after taking drying is placed in 15mL vial, is then added
8mL electrolyte (1M LiPF6, EC:DMC:EMC=1:1:1), it is stirred 1 day in glove box, with DME centrifuge washing, and lazy
Property protection gas Ar atmosphere under room temperature in vacuo is dry, grinding, it is final to obtain activation M-TpBD nano particle.
The acquisition of the composite solid electrolyte film of PEO cladding activation nano particle:
Powder polymer P EO is weighed respectively and activation M-TpBD nano particle 25mg, 75mg are placed in mortar, is ground
3min.Then room temperature suppresses 3min under 4MPa pressure, forms the composite solid electrolyte film with PEO cladding M-TpBD.
The present embodiment prepares the composite solid electrolyte film room-temperature conductivity of PEO cladding M-TpBD up to 10-4S cm-1。
Embodiment 5:
As different from Example 4, the ingredient of liquid electrolyte is different for the present embodiment, to constitute a kind of composite solid electricity
Xie Zhi, liquid electrolyte is by PEG (Mw, 600), DME, LiN (SO in the composite solid electrolyte film2CF3)2It constitutes, activates M-
The mass ratio of TpBD nano particle and polymer P EO are 70:30；The wherein mass ratio of nano particle M-TpBD and liquid electrolyte
For 35:35.
Activate the acquisition of nano particle:
(1) preparation of liquid electrolyte
It takes DME, PEG 9mL, 1mL to be mixed in vial in glove box respectively and stirs 6h, be sufficiently mixed uniformly.So
Afterwards, 2.89g LiN (SO is added2CF3)2(LTFSI) it is configured to the liquid electrolyte of 1mol.
(2) preparation of M-TpBD material is activated
In glove box, the M-TpBD powder granule 200mg after taking drying is placed in 10mL vial, is then added
The liquid electrolyte of the above-mentioned configuration of 7mL, the stirring stirring 36h in glove box protect gas Ar with DME centrifuge washing, and in inertia
Room temperature in vacuo is dry under atmosphere, grinds, final to obtain activation M-TpBD nano particle.
The acquisition of the composite solid electrolyte film of PEO cladding activation nano particle:
Weigh powder polymer P EO and activation M-TpBD nano particle respectively 30mg, 70mg be placed in mortar, grind
3min.Then room temperature suppresses 3min under 4MPa pressure, forms the composite solid electrolyte film with PEO cladding M-TpBD.
The M-TpBD composite solid electrolyte film room-temperature conductivity of PEO manufactured in the present embodiment cladding is up to 10-5Scm-1。
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art are not departing from the principle of the present invention and objective
In the case where can make changes, modifications, alterations, and variations to the above described embodiments within the scope of the invention.
Claims (9)
1. a kind of composite solid electrolyte of PEO cladding activation nano particle, which is characterized in that composite solid electrolyte is by quality
Percentage 60-90% activates nano particle, 10-40% polymer P EO is constituted；Wherein activation nano particle is then by accounting for composite solid
The liquid electrolyte of electrolyte gross mass percentage 20-40% nano particle and 30-50% are constituted.
2. the composite solid electrolyte of PEO cladding activation nano particle as described in claim 1, which is characterized in that the nanometer
Particle is that the caged porous nanometer material with topological structure is constituted；
Preferably, the material of the nano particle is one of ZIF, MOF, COF, molecular sieve or a variety of.
3. the composite solid electrolyte of PEO cladding activation nano particle as described in claim 1, which is characterized in that the liquid
Electrolyte is made of alkali metal salt and solvent；
Preferably, the alkali metal salt is LiPF6、LiAsF6、LiBF4、LiClO4、LiN(SO2CF3)2、LiCF3SO3One of
Or it is a variety of；
Optional, the solvent is one of EC, DMC, EMC, FEC, TEGDME, DME, VC, DMSO, PC, PEG, DOL or more
Kind.
4. a kind of preparation side of the composite solid electrolyte of the cladding of the PEO as described in claim any one of 1-3 activation nano particle
Method, which is characterized in that
It activates the acquisition of nano particle: vacuum drying nano particle being dissolved in organic solvent with alkali metal salt in glove box and is obtained
The liquid electrolyte arrived is mixed according to the ratio of 20-50g/L, and stirring makes liquid electrolyte well into nano-porous materials
Duct in, rear centrifugation, washing, room temperature in vacuo is dry under inert gas shielding atmosphere again, until become powder state, wherein
The 10-30wt.% of totality powder quality shared by liquid electrolyte, after ground in glove box；It is preferred that grinding 10-30min, obtains
Activate nano particle；
The acquisition of the composite solid electrolyte film of PEO cladding activation nano particle: by polymer P EO and resulting activation nanometer
Grinding keeps PEO fully dispersed into activation nano particle after grain mixing；It is preferred that grinding 10-20min；Use hydraulic press at room temperature afterwards
Compacting.
5. preparation method as claimed in claim 4, which is characterized in that in the acquisition step of the activation nano particle, the liquid
Concentration in state electrolyte containing alkali metal salt soln is 0.5-2mol/L.
6. preparation method as claimed in claim 4, which is characterized in that described true in the acquisition step of the activation nano particle
Moisture content is less than 0.1% in the dry nano-porous materials of sky；Preferably, it is done at 60-150 DEG C by nano-porous materials
It is dry to make in nano-porous materials moisture content less than 0.1%.
7. preparation method as claimed in claim 4, which is characterized in that described lazy in the acquisition step of the activation nano particle
Property gas atmosphere under inert gas be high-purity Ar atmosphere；
Optional, the room temperature under the inert gas shielding atmosphere in room temperature in vacuo drying is 20-40 DEG C.
8. preparation method as claimed in claim 4, which is characterized in that the composite solid electricity of the PEO cladding activation nano particle
In the acquisition step for solving plasma membrane, the pressure that the hydraulic press compacting uses is 3-15MPa.
9. preparation method as claimed in claim 4, which is characterized in that the composite solid electricity of the PEO cladding activation nano particle
Solve plasma membrane acquisition step in, the compacting with a thickness of 40-220 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910857634.1A CN110518279B (en) | 2019-09-09 | 2019-09-09 | Composite solid electrolyte of PEO-coated activated nanoparticles and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910857634.1A CN110518279B (en) | 2019-09-09 | 2019-09-09 | Composite solid electrolyte of PEO-coated activated nanoparticles and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110518279A true CN110518279A (en) | 2019-11-29 |
| CN110518279B CN110518279B (en) | 2021-11-23 |
Family
ID=68631902
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910857634.1A Active CN110518279B (en) | 2019-09-09 | 2019-09-09 | Composite solid electrolyte of PEO-coated activated nanoparticles and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110518279B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112072176A (en) * | 2020-09-28 | 2020-12-11 | 中北大学 | Single-ion nano composite solid electrolyte and preparation method thereof |
| CN112687946A (en) * | 2020-12-23 | 2021-04-20 | 北京理工大学前沿技术研究院 | Method for preparing functional inorganic solid electrolyte powder by vacuum coating technology |
| WO2021189161A1 (en) * | 2020-03-22 | 2021-09-30 | Solid Ultrabattery Inc. | All solid-state electrolyte composite based on functionalized metal-organic framework materials for li thoum secondary battery and method for manufacturing the same |
| CN114551791A (en) * | 2021-07-29 | 2022-05-27 | 万向一二三股份公司 | Composite positive plate containing single crystal high nickel positive electrode material and all-solid-state battery |
| WO2022190648A1 (en) * | 2021-03-11 | 2022-09-15 | 株式会社村田製作所 | Non-aqueous electrolyte, and electrochemical device |
| JP7424488B2 (en) | 2020-06-23 | 2024-01-30 | 株式会社村田製作所 | electrochemical device |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1640934A (en) * | 2004-12-16 | 2005-07-20 | 上海交通大学 | Full-solid composite polymer electrolyte containing molecular sieve and preparation method therefor |
| CN103474696A (en) * | 2013-08-27 | 2013-12-25 | 中南大学 | Organic-inorganic hybrid polymeric solid electrolyte material and application thereof |
| CN103834153A (en) * | 2012-11-27 | 2014-06-04 | 海洋王照明科技股份有限公司 | Gel polymer electrolyte and preparation method thereof |
| US9142863B2 (en) * | 2009-01-15 | 2015-09-22 | Cornell University | Nanoparticle organic hybrid materials (NOHMs) and compositions and uses of NOHMs |
| CN106450512A (en) * | 2016-09-29 | 2017-02-22 | 清华大学 | Metal battery with molecular sieve solid electrolyte layer |
| CN108878970A (en) * | 2018-06-29 | 2018-11-23 | 华中科技大学 | A kind of composition polymer solid electrolyte, solid state lithium battery and preparation method thereof |
| CN109301313A (en) * | 2018-10-08 | 2019-02-01 | 北京理工大学 | Sodium ion quasi-solid electrolyte and preparation method thereof |
| CN109888373A (en) * | 2018-12-27 | 2019-06-14 | 山东大学 | A kind of organic/inorganic composite solid electrolyte and preparation method thereof |
-
2019
- 2019-09-09 CN CN201910857634.1A patent/CN110518279B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1640934A (en) * | 2004-12-16 | 2005-07-20 | 上海交通大学 | Full-solid composite polymer electrolyte containing molecular sieve and preparation method therefor |
| US9142863B2 (en) * | 2009-01-15 | 2015-09-22 | Cornell University | Nanoparticle organic hybrid materials (NOHMs) and compositions and uses of NOHMs |
| CN103834153A (en) * | 2012-11-27 | 2014-06-04 | 海洋王照明科技股份有限公司 | Gel polymer electrolyte and preparation method thereof |
| CN103474696A (en) * | 2013-08-27 | 2013-12-25 | 中南大学 | Organic-inorganic hybrid polymeric solid electrolyte material and application thereof |
| CN106450512A (en) * | 2016-09-29 | 2017-02-22 | 清华大学 | Metal battery with molecular sieve solid electrolyte layer |
| CN108878970A (en) * | 2018-06-29 | 2018-11-23 | 华中科技大学 | A kind of composition polymer solid electrolyte, solid state lithium battery and preparation method thereof |
| CN109301313A (en) * | 2018-10-08 | 2019-02-01 | 北京理工大学 | Sodium ion quasi-solid electrolyte and preparation method thereof |
| CN109888373A (en) * | 2018-12-27 | 2019-06-14 | 山东大学 | A kind of organic/inorganic composite solid electrolyte and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| R. SENTHIL KUMAR等: "Metal organic framework-laden composite polymer electrolytes for efficient and durable all solid-state-lithium batteries", 《RSC ADVANCES》 * |
| 许金梅等: "PEO10-LiClO4/mSBA-15复合全固态聚合物电解质的制备和表征", 《第十三次全国电化学会议论文文摘要集（上集）》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021189161A1 (en) * | 2020-03-22 | 2021-09-30 | Solid Ultrabattery Inc. | All solid-state electrolyte composite based on functionalized metal-organic framework materials for li thoum secondary battery and method for manufacturing the same |
| JP7424488B2 (en) | 2020-06-23 | 2024-01-30 | 株式会社村田製作所 | electrochemical device |
| CN112072176A (en) * | 2020-09-28 | 2020-12-11 | 中北大学 | Single-ion nano composite solid electrolyte and preparation method thereof |
| CN112687946A (en) * | 2020-12-23 | 2021-04-20 | 北京理工大学前沿技术研究院 | Method for preparing functional inorganic solid electrolyte powder by vacuum coating technology |
| CN112687946B (en) * | 2020-12-23 | 2022-01-07 | 北京理工大学前沿技术研究院 | Method for preparing functional inorganic solid electrolyte powder by vacuum coating technology |
| WO2022190648A1 (en) * | 2021-03-11 | 2022-09-15 | 株式会社村田製作所 | Non-aqueous electrolyte, and electrochemical device |
| CN114551791A (en) * | 2021-07-29 | 2022-05-27 | 万向一二三股份公司 | Composite positive plate containing single crystal high nickel positive electrode material and all-solid-state battery |
| CN114551791B (en) * | 2021-07-29 | 2024-02-02 | 万向一二三股份公司 | Composite positive plate containing monocrystal high-nickel positive electrode material and all-solid-state battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110518279B (en) | 2021-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110518279A (en) | A kind of composite solid electrolyte and preparation method thereof of PEO cladding activation nano particle | |
| EP3968407B1 (en) | Secondary battery, process for preparing same, and apparatus comprising secondary battery | |
| CN106537679B (en) | All solid state secondary battery and its manufacturing method, inorganic solid electrolyte particle, solid electrolyte composition, battery electrode sheet | |
| Lee et al. | Electrochemical performance of lithium/sulfur batteries with protected Li anodes | |
| Chen et al. | Chitosan as a functional additive for high-performance lithium–sulfur batteries | |
| JP5682970B2 (en) | Positive electrode active material, positive electrode including the same, and lithium secondary battery | |
| CN112701348B (en) | Polymer solid electrolyte, all-solid lithium battery and preparation method thereof | |
| CN1157817C (en) | Compound polymer dielectric membrane and lithium batttery made by using said membrane | |
| CN108370061A (en) | Solid electrolyte composition, binder particles, solid state secondary battery piece, solid state secondary battery electrode slice and solid state secondary battery and their manufacturing method | |
| JP2018525774A (en) | Lithium ion gel battery | |
| CN108899579A (en) | A kind of all-solid lithium-ion battery of self-crosslinking composite solid electrolyte prepared and its constitute | |
| CN107591511A (en) | Composite film material for lithium battery and its preparation method and application | |
| CN106233512A (en) | Modified guaran urea binding agent for lithium ion battery | |
| Wang et al. | Integrated design of aqueous zinc-ion batteries based on dendrite-free zinc microspheres/carbon nanotubes/nanocellulose composite film anode | |
| CN107403920A (en) | A kind of silicon-carbon combination electrode and preparation method thereof | |
| EP3637523A1 (en) | Gelatinized system containing ether compounds, and preparation method therefor and applications thereof | |
| CN103840112A (en) | PVDF-HFP-based composite porous polymer diaphragm and preparation method thereof | |
| CN105355819A (en) | Lithium-rich manganese-based high-energy-density lithium-ion battery and preparation method thereof | |
| CN109148946A (en) | A kind of three-dimensional manometer skeleton composite gel electrolyte material and its preparation method and application | |
| CN109599561A (en) | Binder for all-solid-state lithium ion secondary battery, electrolyte membrane, electrode membrane, battery and preparation method | |
| Kubarkov et al. | Poly (3, 4-ethylenedioxythiophene): poly (styrenesulfonic acid)–polymer composites as functional cathode binders for high power LiFePO 4 batteries | |
| CN109411716A (en) | Based lithium-ion battery positive plate and preparation method thereof and lithium ion battery | |
| CN114730910A (en) | Secondary battery, preparation method thereof, battery module comprising secondary battery, battery pack and device | |
| ES2488718T3 (en) | Lithium Accumulator Electrode | |
| CN110459723A (en) | Battery diaphragm and preparation method thereof and battery with the battery diaphragm |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |