CN109921024A - A kind of flexible solid lithium ion conductor and preparation method thereof applied to battery - Google Patents
A kind of flexible solid lithium ion conductor and preparation method thereof applied to battery Download PDFInfo
- Publication number
- CN109921024A CN109921024A CN201910185272.6A CN201910185272A CN109921024A CN 109921024 A CN109921024 A CN 109921024A CN 201910185272 A CN201910185272 A CN 201910185272A CN 109921024 A CN109921024 A CN 109921024A
- Authority
- CN
- China
- Prior art keywords
- lithium ion
- lithium
- battery
- ion conductor
- polymer
- 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
-
- 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
- Conductive Materials (AREA)
- Secondary Cells (AREA)
Abstract
The present invention provides a kind of flexible solid lithium ion conductor and preparation method thereof, belongs to energy stores and transition material technical field.The flexible lithium ion conductor includes at least two kinds of components containing lithium ion, wherein: a component is inorganic or organic lithium salts, another component is polymer, at least one on main chain with ether-oxygen bond, carbon nitrogen singly-bound, C=O bond or silicon oxygen bond, and contain the lithium ion being coordinated with ionic bond.Solid lithium ion conductors of the invention are the flexible body with plasticity, conductivity at room temperature > 10‑4S/cm, lithium ion transference number > 0.4.Flexible solid lithium ion conductor of the invention is applied in the solid state battery including lithium ion battery, lithium metal battery, lithium-sulfur cell and lithium-air battery, due to high-lithium ion conductivity, high tensile strength and certain plastic deformation ability, it can be used as binder and introduce electrode, or it is used as solid electrolyte simultaneously, excellent interface stability and cycle life is presented.
Description
Technical field
The invention belongs to energy stores and transition material technical field, in particular to a kind of solid lithium ion conductors flexible
And preparation method, and its application as binder and electrolyte in the battery.
Background technique
Lithium ion conductor be can conducting lithium ions and the substance of electronic isolation, in lithium ion battery, lithium metal battery, lithium sulphur
The important medium of lithium ion conduction in battery and lithium-air battery is the critical material for ensureing normal battery operation.Currently, universal
The lithium ion conductor of use is liquid, plays in liquid system that lithium ion mobility rate is fast, conductivity is high by (>=10-3S/cm)
Advantage, and liquid lithium ion conductor have mobility, can impregnating porous electrode, thus in the battery building lithium ion pass
The continuous passage led, therefore the lithium ion conductor of liquid applies maturation in energy stores and conversion equipment.But liquid lithium from
Sub- conductor application limit battery energy density further increase and the flexible design of cell shapes, especially semi-open
Volatilization with liquid lithium ion conductor in the lithium-air battery of Full-open, which is dried up, directly results in battery failure.Moreover, even more serious
Be thus bring security risk, such as volatilization burning, leakage cause explosion etc. accidents.Solid lithium ion conductors can not only gram
The shortcomings that taking liquid system, and the lower solid lithium ion conductors of density with plasticity can prepare flexibly and fracture toughness is excellent
It is different, it ensure that the diversification of battery design, substantially reduce manufacturing cost, improve the energy density of lithium ion battery.Therefore, flexible
Solid lithium ion conductors are considered as a kind of important material for being most hopeful to break through the exploitation of more secure and reliable higher energy densitybattery
Material.
Currently, solid lithium ion conductors are often rigid, lack plastic deformation ability.In the prior art, it is common that
Certain polymer is mixed into the solid lithium ion conductors such as organic lithium salt and inorganic lithium salt to increase flexibility, but is increasing polymer
While content, it cannot be considered in terms of the performances such as the lithium ion conductivity, lithium ion transference number and plastic deformation ability of system.These
The dissociation in the polymer of performance and solid lithium ion conductors and migration are directly related, and by solid lithium ion conductors and polymer
Type and interaction between the two determined.In addition to organic lithium salt and inorganic lithium salt, lithium single ion conductor is also
Solid lithium ion conductors, and some single ion conductors are polymer, but the conductivity of single ion conductor polymer is general at present
All over lower, conductivity at room temperature is 10-5~10-8Within the scope of S/cm.[the Jounal of such as Geiculescu
Electrochemical Society, 2004,151 (9): A1363-1368] it synthesizes containing oroalkane sulfonyl imines of enjoying a double blessing
The lithium single ion conductor of anion structure unit, even if room-temperature conductivity is blended with PEO still down to 10-7S/cm；Bouchet and
Armand etc. [Natrue Material, 2013,12:452] has synthesized polymer lithium single ion conductor P (STFSILi)-b-
PEO-b-P (STFSILi), conductivity is about 1.3 × 10 at 60 DEG C-5S/cm.The base proposed in patent ZL201310302904.5
Reach 10 in the conductivity at room temperature of polyvinyl formal or all solid state polyelectrolyte membrane of its homologue-6S/cm.Cause
This, need at present development be provided simultaneously with the lithium of high-lithium ion conductivity, high-lithium ion transport number, high mechanical strength and high-ductility from
Sub- conductor material is high-energy density and high security lithium ion battery, lithium metal battery, lithium-sulfur cell and lithium-air battery
Design and development provide critical material.
Summary of the invention
The object of the present invention is to provide a kind of flexible solid lithium ion conductors, are provided simultaneously with high-lithium ion conductivity, height
Lithium ion transference number, high mechanical strength and high-ductility, and the application as binders for electrodes and electrolyte in the battery.
A kind of flexible solid lithium ion conductor provided by the invention includes at least following two containing the component of lithium ion:
Lithium salts and polymer.The lithium salts is organic lithium salt, has the combination energy lower than 515 kJ/mol.The polymer has
General formula structure (1):
(1)
R in its general structure (1)1And R2Independently of each other, R1At least one containing following group: ether-oxygen bond (- C-O-C-),
Carbon nitrogen singly-bound (- C-N-), C=O bond (- C=O-) or silicon oxygen bond (- Si-O-)；Lithium ion is bonded on R2 by ionic bond, and
1 x:y≤4 <.Wherein, organic lithium salt contains boryl, sulfonic group, phosphate or imido grpup, and relative molecular mass is greater than 143 and is less than
470.And particularly preferably from least one LiODFB, LiBOB, LiCF of following substance3SO3、LiN(SO2CF3)2、LiN
(SO2C2F5)2、Li(C2F5)3PF3、LiN(FSO2)2、ddCTP-Li3。
A kind of flexible solid lithium ion conductor provided by the invention, preparation method includes the following steps: polymer is filled
It point is dissolved into organic solvent, adds organic lithium salt and reach abundant dissolution, form solution, wherein polymer and organic lithium salt
Ratio reaches: the molar ratio of the lithium ion content of the content and organic lithium salt of functional group R1 is 5:1- in Polymer Formulation structure 1
50:1；Then solution is heated to 40-120 DEG C, stirs 2-36h, obtains slurry；Finally, slurry is placed at 40 DEG C -100 DEG C,
Forced air drying or vacuum drying；Or uniformly coat slurry or tape casting, it is finally placed it at 40 DEG C -100 DEG C again, drum
Air-dry dry or vacuum drying.
A kind of flexible solid lithium ion conductor provided by the invention is as disposable lithium-battery, secondary lithium battery or secondary
The binder of the positive or negative pole of lithium metal battery；Perhaps solid state battery is used as the electrolyte of solid state battery or simultaneously
Positive or negative pole binder and electrolyte.
The invention has the following advantages that
Polymer in flexible solid lithium ion conductor of the present invention contains the lithium ion being bonded with ionic bond, simultaneously
At least one containing ether-oxygen bond (- C-O-C-), carbon nitrogen singly-bound (- C-N-), C=O bond (- C=O-) or silicon oxygen bond (- Si-O-)
Kind, there is strong dissolution lithium salts and the coordination ability with lithium ion, for example, since oxygen element is stronger in-C-O-C- ether-oxygen bond
Electronegativity, so that carbon-oxygen chemical key is shown as polar covalent bond, shared electron opposite direction oxygen atom deviates, so that the oxygen of ether-oxygen bond
There is stronger electron donation, while oxygen atom has two pairs of lone pair electrons on atom, so that ether oxygen base has lithium ion
Strong coordination ability.In turn, the high-efficiency dissolution of the component-lithium salts for containing lithium ion for another in the polymer creates condition.
R in the polymers compositions of solid lithium ion conductors flexible of the present invention1And R2Independently of each other, R1With R2Mole
Than x:y in 1 range of < x:y≤4, the locomitivity of polymer molecule has been ensured.If R1With R2Ratio excessively high go beyond the scope
When, solvation simultaneously assists Li+The structural unit of transmission is too low, causes ionic conductivity relatively low；If R1With R2Ratio it is too low when,
Cause lithium ion transference number relatively low.With general structure (1) and reach the polymer of corresponding requirements, guarantee plurality of group with
One lithium ion generates association-dissociation, continuous lithium ion transport channel is formed, to promote the migration of lithium ion.
Another component is organic lithium salt in flexible solid lithium ion conductor of the present invention, has and is lower than 515 kJ/
The combination energy of mol has ensured the dissolution and dissociation of lithium salts in the polymer.Moreover, the R in polymer1Polar groups are deposited
Chemical environment is created in the dissolution of more lithium salts in the polymer.Flexible solid lithium ion conductor of the present invention is from system
Component constitutes and two angles of interaction, solves the concentration of the i.e. transportable lithium ion of carrier in current polymeric system
The technical problem being difficult to improve.And lithium salts is dissolved in the polymers compositions of system, free anion reduces polymerization
The intermolecular active force with intramolecular of object, improves the locomitivity of segment, has ensured the transmittability of carrier.In summary special
Sign, flexible solid lithium ion conductor of the present invention, which has reached, is provided simultaneously with conductivity at room temperature higher than 10-4S/cm, lithium
Transference number of ions is greater than the performance advantage of 0.4, the tensile strength higher than 15 MPa and the plastic deformation greater than 30%.Solves mesh
Preceding lithium ion conductor cannot be considered in terms of the technical problem of lithium ion conductivity, lithium ion transference number and plastic deformation ability.
Flexible solid lithium ion conductor of the present invention is as the binder of anode or cathode, the electricity of solid state battery
Xie Zhi, or the binder and electrolyte as the positive or negative pole of solid state battery simultaneously, significantly improve the energy density of battery
And cycle life.
Detailed description of the invention
Fig. 1 is the SEM image of lithium ion conductor prepared by embodiment 1.
Fig. 2 is the SEM image of lithium ion conductor prepared by comparative example 1.
Fig. 3 is the test result that the conductivity of lithium ion conductor prepared by embodiment 2 varies with temperature.
Fig. 4 is electric current-polarization time curve of lithium ion conductor prepared by embodiment 2.
Fig. 5 is the test result that the conductivity of lithium ion conductor prepared by comparative example 2 varies with temperature.
Fig. 6 is electric current-polarization time curve of lithium ion conductor prepared by comparative example 2.
Fig. 7 is tensile strength-strain curve of lithium ion conductor prepared by embodiment 3.
Fig. 8 be embodiment 4 prepare lithium ion conductor as positive electrode binder be assembled into battery after loop test curve.
Specific embodiment:
It will be described in more detail below by embodiment, but protection scope of the present invention is not limited to embodiment.
Embodiment 1
(1) for polymer using single Lithium bis (oxalate) borate grafting polyvinyl alcohol formal, structural formula is as follows, wherein lower x:y=4.
It weighs the above polymer 0.4305g to be dissolved in 2.583g dimethyl sulfoxide, is sufficiently stirred and makes it completely dissolved.
(2) the organic lithium salt LiODFB(relative molecular mass 144 that 0.031g contains boryl is continuously added), corresponding general formula knot
Structure R1(1,3- dioxane) and organic lithium salt LiODFB lithium ion molar ratio be 15:1, formed solution.
(3) solution is then heated to 70 DEG C of stirrings for 24 hours, obtains slurry, then slurry is uniformly coated on glass plate,
It is dried in vacuo at 50 DEG C for 24 hours, obtains flexible solid lithium ion conductor.
Flexible solid lithium ion conductor microstructure obtained by embodiment 1 is as shown in Figure 1, the lithium ion conductor as seen from the figure
For surface compact and uniform film.Lithium ion transference number is 0.67, and room-temperature conductivity is 4.77 × 10-4S/cm, as solid
State electrolyte matches assembling half-cell with iron phosphate lithium electrode, and capacity retention ratio is after recycling 100 times at 55 DEG C, 0.3C
83.9%。
Comparative example 1
(1) for polymer using single Lithium bis (oxalate) borate grafting polyvinyl alcohol, structural formula is as follows, wherein lower x:y=0.Weigh with
Upper polymer 0.4305g is dissolved in 2.583g dimethyl sulfoxide, is sufficiently stirred and is made it completely dissolved.
(2) the organic lithium salt LiODFB that 0.031g contains boryl is continuously added, solution is formed.
(3) solution is then heated to 50 DEG C of stirrings for 24 hours, obtains slurry, then slurry is uniformly coated on glass plate,
It is dried in vacuo at 50 DEG C for 24 hours, obtains solid lithium ion conductors sample.
Lithium ion conductor microstructure obtained by comparative example 1 is as shown in Fig. 2, the lithium ion conductor film surface as seen from the figure
Lithium salt particles precipitation phenomenon is serious, illustrates that dissolution of the organic lithium salt LiODFB in polymeric system is incomplete, remaining is organic
Lithium salts is segregated in lithium ion conductor.And there are macropore appearance, organic lithium salt on lithium ion conductor film obtained by comparative example 1
The dissolution and segregation of LiODFB produces the flexibility and Film Morphology of polymer and seriously affects.Unlike the first embodiment, right
Polymer in ratio 1 does not have general formula structure (1), without containing the R in general structure (1)1Unit, therefore lead to polymer energy
It enough dissolves and the ability for dissociating lithium salts is limited, this is current polymeric system common problem.The resulting lithium of comparative example 1 from
The conductivity at room temperature and lithium ion transference number of sub- conductor are well below the flexible lithium ion conductor that embodiment 1 provides.It is right
Lithium ion conductor prepared by ratio 1 matches assembling half-cell as solid electrolyte with LiFePO4, recycles at 55 DEG C, 0.3C
Battery failure after 7 times, cycle performance can not show a candle to the flexible lithium ion conductor that embodiment 1 is prepared by the method for the invention.
Embodiment 2
(1) polymer uses benzene sulfonic acid lithium grafted polyvinylidene vinyl fluoride, and structural formula is as follows, wherein x:y=1.2:1.It takes above
Polymer 0.7231g is dissolved in 3.32g acetonitrile, is sufficiently stirred and is made it completely dissolved.
(2) the organic lithium salt LiBETI(relative molecular mass 387 that 0.054g has sulfimide moiety is continuously added),
Corresponding general formula structure R1(- CH2-CF2) it with the molar ratio of organic lithium salt LiBETI lithium ion is 50:1, form solution.
(3) solution is then heated to 40 DEG C of stirring 30h, obtains slurry.Finally, slurry is dried in vacuo at 60 DEG C
36h obtains flexible solid lithium ion conductor.
The ac impedance measurement result of flexible solid lithium ion conductor obtained by embodiment 2 is as shown in figure 3, at 25 DEG C of room temperature
Under, the room-temperature conductivity of the lithium ion conductor is 6.84 × 10-4S/cm.If electric current-polarization time curve of Fig. 4 can obtain, implement
The lithium ion transference number of flexible solid lithium ion conductor obtained by example 2 is 0.71.
Comparative example 2
(1) polymer uses benzene sulfonic acid lithium grafted polyvinylidene vinyl fluoride, and structural formula and the polymer phase of embodiment 2 are same, wherein x:y
= 1.2:1.It weighs the above polymer 0.7231g to be dissolved in 3.32g acetonitrile, is sufficiently stirred and makes it completely dissolved.
(2) 0.023g organic lithium salt LiBF is continuously added4(relative molecular mass 93), corresponding general formula structure R1(- CH2-
CF2) and organic lithium salt LiBF4Lithium ion molar ratio be 50:1, formed solution.
(3) solution is then heated to 40 DEG C of stirring 30h, obtains slurry.Finally, slurry is dried in vacuo at 60 DEG C
36h obtains solid lithium ion conductors.
The room-temperature conductivity for the solid lithium ion conductors that comparative example 2 obtains is 1.61 × 10-5S/cm(Fig. 5), lithium ion
Transport number is 0.29(such as Fig. 6).2 difference from Example 2 of comparative example is: organic lithium salt is LiBF in comparative example 24(phase
To molecular mass 93) do not contain the functional groups such as boryl, boryl, sulfonic group, phosphate or imido grpup, the organolithium in embodiment 2
Salt is the organic lithium salt LiBETI(relative molecular mass 387 with sulfimide moiety).
Embodiment 3
(1) polymer is grafted poly- ethylene carbonate using perfluoroalkyl carboxyl lithium, and structural formula is as follows, wherein x:y=2.4:
1.It weighs the above polymer 0.6471g to be dissolved in 2.983g tetrahydrofuran, is sufficiently stirred and makes it completely dissolved.
(2) the organic lithium salt ddCTP-Li that 0.151g contains phosphate group is continuously added3(relative molecular mass 469), it is right
Answer general formula structure R1(- O-CO-O-CH2) and organic lithium salt ddCTP-Li3The molar ratio of lithium ion is 10:1, forms solution.
(3) solution is then heated to 120 DEG C of stirring 2h, obtains slurry, then slurry is uniformly coated on glass plate,
Finally, it is dried in vacuo 36h at 60 DEG C, obtains flexible solid lithium ion conductor.
Solid lithium ion conductors obtained by embodiment 3 have good flexibility；Tensile strength-strain curve as shown in fig. 7,
Its mechanical strength is up to 40MPa, and tensile strain rate is up to 225%.
Embodiment 4
(1) polymer using fluorobenzenesulfonimide lithium be grafted dimethyl polysiloxane, structural formula is as follows, wherein x:y=
2.6:1.It weighs the above polymer 0.2937g to be dissolved in 5.598g N-Methyl pyrrolidone, being sufficiently stirred keeps it completely molten
Solution.
(2) the LiFSI(relative molecular mass 187 that 0.51g contains imine is continuously added), corresponding general formula structure
R1(- Si (CH3)2- O-) it with the molar ratio of the lithium ion of organic lithium salt LiFSI is 5:1, form solution.
(3) solution is then heated to 85 DEG C of stirrings for 24 hours, obtains slurry.Finally, it is dried in vacuo for 24 hours, obtains at 65 DEG C
To flexible solid lithium ion conductor.
The flexible solid lithium ion conductor that embodiment 4 is obtained is as the binder of positive electrode, with acetylene black, ferric phosphate
Lithium is uniformly mixed according to mass ratio 15:10:75, obtains anode slice of lithium ion battery, group after rolling coated in drying on aluminium foil
The cycle performance for filling solid state battery is as shown in Figure 8.Initial discharge specific capacity is 149.8 mAh/g, circulation under room temperature, 0.2C
100 circle 124.7 mAh/g of residue, capacity retention ratio 83.3%, cyclical stability and service life significantly improve.
Claims (5)
1. a kind of flexible solid lithium ion conductor applied to battery, which is characterized in that contain lithium including at least following two
The component of ion: lithium salts and polymer, the lithium salts are organic lithium salts, have the combination energy lower than 515kJ/mol；Described
Polymer has general formula structure (1):
R in its general structure (1)1And R2Independently of each other, R1At least one containing following group: ether-oxygen bond, carbon nitrogen singly-bound,
C=O bond or silicon oxygen bond；Lithium ion is bonded on R2 by ionic bond, and 1 x:y≤4 <.
2. flexible solid lithium ion conductor according to claim 1, which is characterized in that the organic lithium salt containing boryl,
Sulfonic group, phosphate or imido grpup, relative molecular mass are greater than 143 and less than 470.
3. flexible solid lithium ion conductor according to claim 1 or 2, which is characterized in that the organic lithium salt contain with
At least one of lower substance: LiODFB, LiBOB, LiCF3SO3、LiN(SO2CF3)2、LiN(SO2C2F5)2、Li(C2F5)3PF3、
LiN(FSO2)2、ddCTP-Li3。
4. a kind of preparation method of the flexible solid lithium ion conductor described in claim 1 applied to battery, which is characterized in that
The following steps are included: polymer is sufficiently dissolved into organic solvent, adds organic lithium salt and reach abundant dissolution, formed molten
Liquid, wherein the ratio of polymer and organic lithium salt reaches: the content of functional group R1 and organic lithium salt in Polymer Formulation structure 1
The molar ratio of lithium ion content is 5:1-50:1；Then solution is heated to 40-120 DEG C, stirs 2-36h, obtains slurry；Most
Eventually, it is placed at 40 DEG C -100 DEG C, forced air drying or vacuum drying.
5. the purposes of flexible solid lithium ion conductor described in any one of claims 1 to 3 is for disposable lithium-battery, two
The binder of the positive or negative pole of secondary lithium ion battery or secondary metals lithium battery；Electrolyte for solid state battery；Or it is same
When for solid state battery positive or negative pole binder and electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910185272.6A CN109921024B (en) | 2019-03-12 | 2019-03-12 | Flexible solid lithium ion conductor applied to battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910185272.6A CN109921024B (en) | 2019-03-12 | 2019-03-12 | Flexible solid lithium ion conductor applied to battery and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109921024A true CN109921024A (en) | 2019-06-21 |
| CN109921024B CN109921024B (en) | 2020-12-29 |
Family
ID=66964274
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910185272.6A Active CN109921024B (en) | 2019-03-12 | 2019-03-12 | Flexible solid lithium ion conductor applied to battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109921024B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2763037C1 (en) * | 2021-06-09 | 2021-12-27 | Федеральное государственное бюджетное учреждение науки Институт физической химии и электрохимии им. А.Н. Фрумкина Российской академии наук (ИФХЭ РАН) | Solid polymer electrolyte lithium oxygen battery |
| WO2022193543A1 (en) * | 2021-03-18 | 2022-09-22 | 南京博驰新能源股份有限公司 | Solid electrolyte and preparation method therefor |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050156145A1 (en) * | 1995-01-09 | 2005-07-21 | Marie Angelopoulos | Deaggregated electrically conductive polymers and precursors thereof |
| US7820323B1 (en) * | 2006-09-07 | 2010-10-26 | The United States Of America As Represented By The Secretary Of The Army | Metal borate synthesis process |
| CN102306831A (en) * | 2011-08-12 | 2012-01-04 | 上海交通大学 | Gel polymer electrolyte membrane for lithium ion secondary battery and preparation method of gel polymer electrolyte membrane |
| CN103065815A (en) * | 2012-12-31 | 2013-04-24 | 华为技术有限公司 | Electric energy storing thin film and preparation method thereof and electric energy storing device |
| CN103509153A (en) * | 2012-06-15 | 2014-01-15 | 华中科技大学 | Polymer single-ion electrolyte and preparation method thereof |
| CN103907235A (en) * | 2012-05-31 | 2014-07-02 | 株式会社Lg化学 | Lithium secondary battery |
| CN105119012A (en) * | 2015-07-16 | 2015-12-02 | 华南师范大学 | Gel polymer electrolyte for lithium ion battery, and preparation method thereof |
| CN107819156A (en) * | 2017-10-31 | 2018-03-20 | 江汉大学 | The preparation method of fire-retardant type solid polymer electrolyte and the serondary lithium battery containing the solid polymer electrolyte |
| CN109037686A (en) * | 2017-07-17 | 2018-12-18 | 浙江林奈新能源有限公司 | Ionomer for aqueous electrode slurry |
-
2019
- 2019-03-12 CN CN201910185272.6A patent/CN109921024B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050156145A1 (en) * | 1995-01-09 | 2005-07-21 | Marie Angelopoulos | Deaggregated electrically conductive polymers and precursors thereof |
| US7820323B1 (en) * | 2006-09-07 | 2010-10-26 | The United States Of America As Represented By The Secretary Of The Army | Metal borate synthesis process |
| CN102306831A (en) * | 2011-08-12 | 2012-01-04 | 上海交通大学 | Gel polymer electrolyte membrane for lithium ion secondary battery and preparation method of gel polymer electrolyte membrane |
| CN103907235A (en) * | 2012-05-31 | 2014-07-02 | 株式会社Lg化学 | Lithium secondary battery |
| CN103509153A (en) * | 2012-06-15 | 2014-01-15 | 华中科技大学 | Polymer single-ion electrolyte and preparation method thereof |
| CN103065815A (en) * | 2012-12-31 | 2013-04-24 | 华为技术有限公司 | Electric energy storing thin film and preparation method thereof and electric energy storing device |
| CN105119012A (en) * | 2015-07-16 | 2015-12-02 | 华南师范大学 | Gel polymer electrolyte for lithium ion battery, and preparation method thereof |
| CN109037686A (en) * | 2017-07-17 | 2018-12-18 | 浙江林奈新能源有限公司 | Ionomer for aqueous electrode slurry |
| CN107819156A (en) * | 2017-10-31 | 2018-03-20 | 江汉大学 | The preparation method of fire-retardant type solid polymer electrolyte and the serondary lithium battery containing the solid polymer electrolyte |
Non-Patent Citations (2)
| Title |
|---|
| TONG LIU 等: "The PVDF-HFP gel polymer electrolyte for Li-O2 battery", 《SOLID STATE IONICS》 * |
| 关红艳 等: "锂离子电池用凝胶聚合物电解质研究进展", 《高分子材料科学与工程》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022193543A1 (en) * | 2021-03-18 | 2022-09-22 | 南京博驰新能源股份有限公司 | Solid electrolyte and preparation method therefor |
| RU2763037C1 (en) * | 2021-06-09 | 2021-12-27 | Федеральное государственное бюджетное учреждение науки Институт физической химии и электрохимии им. А.Н. Фрумкина Российской академии наук (ИФХЭ РАН) | Solid polymer electrolyte lithium oxygen battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109921024B (en) | 2020-12-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jeong et al. | Revisiting polymeric single lithium-ion conductors as an organic route for all-solid-state lithium ion and metal batteries | |
| Xiang et al. | A flame-retardant polymer electrolyte for high performance lithium metal batteries with an expanded operation temperature | |
| Zhao et al. | Liquid phase therapy to solid electrolyte–electrode interface in solid-state Li metal batteries: a review | |
| Liu et al. | Composition modulation and structure design of inorganic‐in‐polymer composite solid electrolytes for advanced lithium batteries | |
| Che et al. | Electrolyte design strategies and research progress for room-temperature sodium-ion batteries | |
| Judez et al. | Quasi-solid-state electrolytes for lithium sulfur batteries: Advances and perspectives | |
| Ahmed et al. | Remarkable conductivity of a self-healing single-ion conducting polymer electrolyte, poly (ethylene-co-acrylic lithium (fluoro sulfonyl) imide), for all-solid-state Li-ion batteries | |
| Liu et al. | In situ polymerization for integration and interfacial protection towards solid state lithium batteries | |
| Diederichsen et al. | Promising routes to a high Li+ transference number electrolyte for lithium ion batteries | |
| Irfan et al. | Recent advances in high performance conducting solid polymer electrolytes for lithium-ion batteries | |
| CN101087035B (en) | An electrolyte for secondary lithium battery and secondary lithium battery using this electrolyte | |
| CN105745778B (en) | Generate the lithium-sulfur cell of electric current | |
| Aziam et al. | Solid-state electrolytes for beyond lithium-ion batteries: A review | |
| CN107591511A (en) | Composite film material for lithium battery and its preparation method and application | |
| KR20160133310A (en) | Electrolyte composite, and negative electrode and lithium second battery including the electrolyte composite | |
| KR20160118958A (en) | Electrolyte for lithium second battery, and lithium second battery comprising the electrolyte | |
| CN108598564A (en) | A kind of solid polymer electrolyte and its preparation method and application | |
| Rong et al. | UV-cured semi-interpenetrating polymer networks of solid electrolytes for rechargeable lithium metal batteries | |
| CN111740156A (en) | Composite solid electrolyte membrane and preparation method thereof | |
| CN111354976A (en) | Preparation method of composite solid electrolyte and application of composite solid electrolyte in solid lithium ion battery | |
| KR20180072469A (en) | Organic-inorganic composite solid electrolyte, lithium secondary cell comprising the same, and manufacturing method for the lithium secondary cell | |
| JP2023513248A (en) | Surface-modified electrodes, methods of preparation and use in electrochemical cells | |
| CN114335700A (en) | Solid electrolyte membrane and preparation method thereof, secondary battery and preparation method | |
| Yao et al. | 3D poly (vinylidene fluoride–hexafluoropropylen) nanofiber-reinforced PEO-based composite polymer electrolyte for high-voltage lithium metal batteries | |
| Ponnada et al. | History and recent developments in divergent electrolytes towards high-efficiency lithium–sulfur batteries–a review |
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 |