CN106785025B - A kind of sulfonic polymeric object electrolyte and its in-situ preparation method and application - Google Patents
A kind of sulfonic polymeric object electrolyte and its in-situ preparation method and application Download PDFInfo
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- CN106785025B CN106785025B CN201710059631.4A CN201710059631A CN106785025B CN 106785025 B CN106785025 B CN 106785025B CN 201710059631 A CN201710059631 A CN 201710059631A CN 106785025 B CN106785025 B CN 106785025B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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Abstract
The present invention provides a kind of sulfonic polymeric object electrolyte and its in-situ preparation method and application.Preparation method is dissolved the polymer in solvent, and the silane coupling agent for containing-SH is added, forms a film, is then immersed in oxidizing agent solution after the bubble of ultrasonic removing system ,-the SH of end is oxidized to sulfonic group, while silane coupling agent hydrolysis generates SiO2, place into acid solution and be acidified after cleaning, after taking-up, rinsed with deionization, and boiled with boiling and remove remaining acid, place into lithium exchange liquid and carry out lithium exchange, cleaning, drying obtains the polymer dielectric film containing Sulfonic Lithium.The sulfonic polymeric object electrolyte thermal stability and electrochemical properties of preparation are improved, it can be applied in the electrochmical power sources system such as lithium ion battery, meet lithium ion battery high current charge-discharge, while obtaining the effect of single ion conductor, improves the security performance of battery.
Description
Technical field
The present invention relates to electrochemical field, in particular to a kind of sulfonic polymeric object electrolyte and its in-situ preparation method and
Using.
Background technique
Lithium ion battery has the characteristics that high-energy-density, high power, memory-less effect, environmental-friendly, is a kind of green
Electrochmical power source, have good portability, be widely used to the mobile digitals such as mobile phone, laptop, camera product and with
And the fields such as military equipments such as the medical supplies such as pacemaker, ventilator and unmanned plane.However, used in lithium ion battery
Organic liquid electrolyte makes lithium ion battery, and there is security risks, and e.g., the main component of liquid electrolyte is carbonates,
Have the characteristics that volatile, inflammable, reactivity is high, therefore there is the burning even security risks of explosion, and in organic liquor
In body electrolyte, need to add lithium salts for conducting lithium ions, however in order to improve lithium salts in the solubility of electrolyte, general lithium
Salt all has macroanion, allows for lithium ion in this way than anion and is easier solvation, causing lithium ion transference number is only 0.3
Left and right, serious polarization phenomena occurs in charging and discharging, therefore there is security risks in charging process.Currently, main
Solution is to substitute liquid electrolyte using polymer dielectric, is improved by the reactivity etc. for reducing electrolyte and electrode
The security performance of lithium ion battery, and improve lithium ion transference number using single ion conductor substitution lithium salts and improve lithium ion battery
Security performance.Inorganic matter is added in polymer dielectric forms organic inorganic composite polymer electrolyte, it is aobvious due to improving
It writes the raising performances such as polymer dielectric and mechanical stability to have received widespread attention, in terms of lithium single ion conductor, in film
Based on upper grafting sulfonic groups.
Liquid electrolyte solvent can be adsorbed in polymer dielectric, and abundant containing having in sulfonic polymeric acceptor phase
Sulfonic Lithium, lithium ion abundant can be dissociateed, to realize the quick conduction of lithium ion.Organic inorganic composite polymer electricity
Solution matter mainly adds inorganic filler in a polymer matrix, and filler is by forming the object centered on filler with polymer segment
Cross-linked network system is managed, enhances the ability of polymer dispersive stress, improves the mechanical performance and thermal stability of polymer dielectric.
If sulfonic acid group can be introduced while filling inorganic filler, may be implemented containing sulfonic organo-mineral complexing
Polymer dielectric function it is compound, and then lithium single ion conductor polymer film is obtained, to improve the comprehensive of polymer dielectric
Close performance.
Summary of the invention
The first object of the present invention is to provide a kind of original containing sulfonic organic inorganic composite polymer electrolyte
Position preparation method, comprising the following steps:
1) polymer solution for forming that mass fraction is 5%~30% is dissolved the polymer in solvent, is added and contains-SH
The silane coupling agent of base, the bubble and film forming of ultrasonic removing system, obtain the polymer with a thickness of 1-100 μm after mixing
Film；Wherein the polymer is polymethyl methacrylate (PMMA), polyacrylonitrile (PAN), Kynoar (PVDF), gathers partially
At least one of viton copolymers (P (VDF-HFP)), the solvent is the good solvent of the polymer；
2) obtained polymer film is immersed into 0.3~6h in oxidizing agent solution ,-SH base in film is made to be oxidized to-SO3H base, together
When silane coupling agent hydrolysis generate SiO2, to be contained-SO3The SiO of H base2Inorganic whisker polymer film, by going
It immerses after ionized water elution in the acid solution of 0.01~12M and further protonates, then eluted with deionized water and boil removing and is residual
The acid stayed obtains sulfonic polymeric object film；
3) sulfonic polymeric object film is immersed concentration is 0.01mol L-1Lithium exchange liquid in carry out lithium exchange, then spend
Ionized water is rinsed and is boiled, and drying obtains the sulfonic polymeric object electrolyte containing Sulfonic Lithium.
It preferably, further include the inorganic Louis that 0.1-5% mass fraction is added into the polymer solution in step 1)
This sour dissociation to promote lithium ion；The inorganic lewis acid is selected from nanoscale aluminum oxide (Al2O3), silica
(SiO2), calcium oxide (CaO), magnesia (MgO), lithium fluoride (LiF), titanium dioxide (TiO2At least one of).
Preferably, in step 1), the film forming is by mixed solution in being cast or scratching in substrate, then in 40~100
0.5~50h of drying and stripping group bottom forms the polymer film under DEG C vacuum condition, wherein the substrate is glass plate or poly- four
Vinyl fluoride plate.
Preferably, in step 1), the film forming is that mixed solution is obtained non-woven polymers film by spinning.
Preferably, in step 1), the good solvent of the polymer is N-Methyl pyrrolidone (NMP) or N, N- dimethyl methyl
Amide (DMF).
Preferably, in step 2), the oxidizing agent solution is hydrogen peroxide (H2O2), nitric acid (HNO3), potassium permanganate
(KMnO4), potassium bichromate (K2Cr2O7) or hypochlorous acid (HClO).
Preferably, in step 2), the acid solution is at least one of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid.
Preferably, in step 3), the lithium exchange liquid is lithium acetate (CH3COOLi), lithium nitrate (LiNO3), lithium sulfate
(Li2SO4), lithium metasilicate (Li2SiO3), the water or ethanol solution of at least one of lithium hydroxide (LiOH).
The second object of the present invention is to provide the sulfonic polymeric object electrolyte of above method preparation.
The third object of the present invention is to provide above-mentioned sulfonic polymeric object electrolyte and changes in lithium ion battery, lithium-sulfur cell etc.
Learn the application of power supply system.The wherein SiO that silane coupling agent in-situ hydrolysis generates2As inorganic filler, cation can fill
Work as lewis acid, with Li+Competition, instead of Li+Lewis Acids and Bases effect occurs with groups such as O on polymer segment, not only inhibits
The recrystallization of polymer, the crystallinity for reducing polymer increase in addition, this competition further promotes the dissociation of Li salt
The number of free carrier.And O etc. then serves as lewis base, with lewis acid Li+It interacts, forms filler Li+It is rich
Phase, and form Li+The new tunnel of migration.Thus obtain higher conductivity at room temperature and Li+Transport number.Therefore, in situ raw
At the effect of filler mainly pass through this phase of the interaction realization of filler and polymer, filler and electrolyte and lithium salts
Interaction can be attributed to a kind of interface behavior.Form the performance that continuous interface is conducive to filler function.Filler/cation
Fu Xiang, phase interface are considered as the new tunnel of electrolytic salt cation transport.Studies have shown that the fast of ion may be implemented in the channel
Speed conduction, to obtain higher conductivity at room temperature and cation transport number.The introducing of inorganic filler can also play stabilization
The effect of electrolyte/electrode interface, improves the electrochemical window of electrolyte system.Remain in this is because inorganic filler can capture
Impurity in electrolyte, such as the water of oxygen, trace, with guard electrode.Therefore, continuous, effective filler/electrolytic salt is formed
The interface of cation is particularly important for the performance for improving electrolyte system.Furthermore it is preferred that, it is improvement effect, it also can be simultaneously
Inorganic filler is additionally incorporated to improve its concentration.
The beneficial effects of the present invention are:
1. polymer solution is uniform solution, it is uniformly mixed, the inorganic phase occurred with organic mixed solution point will not occurs
Solve phenomenon, coupling agent generated in-situ SiO in film2It can be distributed more uniform.
2. realizing inorganic filler and sulfonic synchronous introducing, method is simple and efficient.Polymer dielectric obtained
Thermal stability, electrochemical properties and the electrochemical properties using the battery of the polymer dielectric are improved.
3. directly use contain end group be-SH coupling agent as-SO3The source H avoids the grafting-on organic polymer
SO3The embrittlement of H, avoids in SiO2Grafting-SO3The too low drawback of H grafting rate, available toughness is preferable, and contain and enrich-
SO3The polymer dielectric film of Li.After impregnating plasticising using electrolyte solvents such as EC, DMC ,-SO can be made3Li, which is ionized out, to be enriched
Lithium ion, the polymer dielectric film of available high-lithium ion conductance meets lithium ion battery high current charge-discharge, simultaneously
The effect of single ion conductor is obtained, the security performance of battery is improved.
4. the in situ of inorganic oxide introduces the thermal stability that can also improve polymer dielectric.
Detailed description of the invention
Fig. 1 is the sulfonic polymeric object dielectric film of embodiment 2 through liquid nitrogen treated cross-sectional scans electron microscope.
Fig. 2 is that the Kynoar for not adding 3-mercaptopropyi trimethoxy silane-hexafluoropropene film of embodiment 2 is red
Outer absorption spectrogram.
Fig. 3 is embodiment 2 after in 80 DEG C of vacuum drying ovens dry 12, the polymer film of the obtained base Han-SH it is infrared
Absorb spectrogram.
Fig. 4 is embodiment 2 after 60 DEG C of drying in vacuum drying oven, the obtained Inorganic whisker containing Sulfonic Lithium
The infrared absorption spectra of sulfonic polymeric object dielectric film.
Fig. 5 is embodiment 2 after 60 DEG C of drying in vacuum drying oven, the obtained Inorganic whisker containing Sulfonic Lithium
The EDS-mapping of sulfonic polymeric object dielectric film schemes.
Specific embodiment
It elaborates below in conjunction with examples and drawings to a specific embodiment of the invention.
Embodiment 1
5g Kynoar powder is dissolved in 45g N-Methyl pyrrolidone, after being completely dissolved, 5g 3- sulfydryl is added
Propyl trimethoxy silicane takes 0.5mL to be coated on the glass slide of 25.4mm × 76.2mm after stirring keeps its mixing full and uniform
On, dry 12h is placed in 80 DEG C of vacuum drying ovens.Up to the polymer film of the base Han-SH.
The polymer film containing-SH base of preparation is immersed to 35% H2O2In solution, 6h is aoxidized under the conditions of 65 DEG C, together
When make silane hydrolyzate, obtain surface and contain-SO3The SiO of H2Inorganic whisker polymer film takes out composite polymeric film, spends
Ionized water elutes three times.Again 0.2M H will be placed in by pretreated composite polymeric film2SO4It is acidified 1h in solution, uses deionization
Water elutes three times, after film boiled into 1h into the water.The composite polymeric film of acidification is placed to 1M CH again3In COOLi solution
Carry out lithium and exchange 12h, deionized water elutes three times, after film boiled into 1h into the water.It is put into vacuum drying oven and dries for 60 DEG C
To the sulfonic polymeric object dielectric film of the Inorganic whisker containing Sulfonic Lithium.
Embodiment 2
5g Kynoar-hexafluoropropylene copolymer powder is dissolved in 45g N-Methyl pyrrolidone, is completely dissolved
Afterwards, 5g 3-mercaptopropyi trimethoxy silane is added, while 2g 10%HNO is added3, to promote 3- mercaptopropyi trimethoxy
The hydrolysis of silane, while playing the role of preliminary oxidation, after stirring keeps its mixing full and uniform, 0.5mL is taken to be coated on 25.4mm
On the glass slide of × 76.2mm, under the conditions of 25 DEG C, relative humidity 50%RH, dry 12h is placed in 80 DEG C of vacuum drying ovens.To obtain the final product
The polymer film of the base containing-SH.
The polymer film containing-SH base of preparation is immersed to 35% H2O2In solution, 6h is aoxidized under the conditions of 65 DEG C, together
When make silane hydrolyzate, obtain surface and contain-SO3The SiO of H2Inorganic whisker polymer film takes out composite polymeric film, spends
Ionized water elutes three times.Again 0.2M H will be placed in by pretreated composite polymeric film2SO4It is acidified 1h in solution, uses deionization
Water elutes three times, after film boiled into 1h into the water.The composite polymeric film of acidification is placed to 1M CH again3In COOLi solution
Carry out lithium and exchange 12h, deionized water elutes three times, after film boiled into 1h into the water.It is put into vacuum drying oven and dries for 60 DEG C
To the sulfonic polymeric object dielectric film of the Inorganic whisker containing Sulfonic Lithium.
Fig. 1 is sulfonic polymeric object dielectric film obtained through liquid nitrogen treated cross-sectional scans electron microscope, therefrom can be with
See nano silica be more evenly distributed in body quite in.Fig. 2,3,4 do not add 3- mercaptopropyi front three respectively
The polymer of the Kynoar of oxysilane-hexafluoropropene film, the base Han-SH obtained after in 80 DEG C of vacuum drying ovens dry 12
The sulfonic polymeric object dielectric film of film, the Inorganic whisker containing Sulfonic Lithium obtained after 60 DEG C of drying in vacuum drying oven
Infrared absorption spectra, it can be seen that in 976cm after oxidation-1Occurs stronger-SO at wave number3-Absorption peak.Fig. 5 is sulphur
The section mapping of acid-based polymer electrolyte, it can be seen that S, Si, O element on the section of sulfonic polymeric object electrolyte
It is uniformly distributed, illustrates-SO in film3It is equally distributed.
Sulfonic polymeric object dielectric film is put into EC/PC (volume ratio 1:1) activation at least 6h, according to ac impedance spectroscopy,
The conductivity for obtaining the sulfonic polymeric object dielectric film reaches 1.08 × 10-4S cm-1. lithium ion transference number reaches 0.92 ±
0.3。
Embodiment 3
5g Kynoar powder is dissolved in 45g N-Methyl pyrrolidone, after being completely dissolved, 5g 3- sulfydryl is added
Propyl trimethoxy silicane is added 1g 100nm aluminum oxide and takes 0.5mL to be coated on after stirring keeps its mixing full and uniform
On the glass slide of 25.4mm × 76.2mm, dry 12h is placed in 80 DEG C of vacuum drying ovens.Up to the polymer film of the base Han-SH.
The polymer film containing-SH base of preparation is immersed to 35% H2O2In solution, 6h is aoxidized under the conditions of 65 DEG C, together
When make silane hydrolyzate, obtain surface and contain-SO3The SiO of H2Inorganic whisker polymer film takes out composite polymeric film, spends
Ionized water elutes three times.Again 0.2M H will be placed in by pretreated composite polymeric film2SO4It is acidified 1h in solution, uses deionization
Water elutes three times, after film boiled into 1h into the water.The composite polymeric film of acidification is placed to 1M CH again3In COOLi solution
Carry out lithium and exchange 12h, deionized water elutes three times, after film boiled into 1h into the water.It is put into vacuum drying oven and dries for 60 DEG C
To the sulfonic polymeric object dielectric film of the Inorganic whisker containing Sulfonic Lithium.
Sulfonic polymeric object dielectric film is put into EC/PC (volume ratio 1:1) activation at least 6h, according to ac impedance spectroscopy,
The conductivity for obtaining the sulfonic polymeric object dielectric film reaches 3.22 × 10-4S cm-1Lithium ion transference number reach 0.93 ±
0.04。
Embodiment 4
5g Kynoar-hexafluoropropylene copolymer powder is dissolved in 45g N-Methyl pyrrolidone, is completely dissolved
Afterwards, be added 5g 3-mercaptopropyi trimethoxy silane, stirring make its mix it is full and uniform after, take 0.5mL be coated on 25.4mm ×
On the glass slide of 76.2mm, dry 12h is placed in 80 DEG C of vacuum drying ovens.Up to the polymer film of the base Han-SH.
The polymer film containing-SH base of preparation is immersed to 35% H2O2In solution, 6h is aoxidized under the conditions of 65 DEG C, together
When make silane hydrolyzate, obtain surface and contain-SO3The SiO of H2Inorganic whisker polymer film takes out composite polymeric film, spends
Ionized water elutes three times.Again 0.2M H will be placed in by pretreated composite polymeric film2SO4It is acidified 1h in solution, uses deionization
Water elutes three times, after film boiled into 1h into the water.The composite polymeric film of acidification is placed to 1M CH again3In COOLi solution
Carry out lithium and exchange 12h, deionized water elutes three times, after film boiled into 1h into the water.It is put into vacuum drying oven and dries for 60 DEG C
To the sulfonic polymeric object dielectric film of the Inorganic whisker containing Sulfonic Lithium.
Embodiment 5
5g Kynoar-hexafluoropropylene copolymer powder is dissolved in 45g N-Methyl pyrrolidone, is completely dissolved
Afterwards, be added 5g 3-mercaptopropyi trimethoxy silane, stirring make its mix it is full and uniform after, on non-woven fabrics machine spinning to get
The non woven cloth in polymer film for the base Han-SH that thickness range is 1-200 μm.By the non woven cloth in polymer film containing-SH base of preparation
Immerse 65% HNO3In solution, 1h is aoxidized, while making silane hydrolyzate, obtain surface and contain-SO3The SiO of H2Inorganic whisker
Polymer film takes out composite polymeric film, three times with deionized water elution.Film is boiled into 1h into the water afterwards.Again by acidification
Composite polymeric film is placed to 1M CH3In COOLi solution carry out lithium exchange 12h, deionized water elute three times, after film is put into
1h is boiled in water.It is put into 60 DEG C of drying in vacuum drying oven and obtains the sulfonic polymeric object electricity of the Inorganic whisker containing Sulfonic Lithium
Solve plasma membrane.
Embodiment 6
A kind of battery, anode use active material LiCoO2, conductive agent selects acetylene black, and bonding agent is using in embodiment 1
Sulfonic polymeric object electrolyte, cathode use active material graphite.
Embodiment 7
A kind of battery, anode use active material LiCoO2, conductive agent selects acetylene black, and bonding agent is using in embodiment 2
Sulfonic polymeric object electrolyte, cathode use active material graphite.
Embodiment 8
A kind of battery, anode use active material LiCoO2, conductive agent selects acetylene black, and bonding agent is using in embodiment 3
Sulfonic polymeric object electrolyte, cathode use active material graphite.
Embodiment 9
A kind of battery, anode use active material LiCoO2, conductive agent selects acetylene black, and bonding agent is using in embodiment 4
Sulfonic polymeric object electrolyte, cathode use active material graphite.
Embodiment 10
A kind of battery, anode use active material LiCoO2, conductive agent selects acetylene black, and bonding agent is using in embodiment 5
Sulfonic polymeric object electrolyte, cathode use active material graphite.
Technical solution of the present invention is described in detail in embodiment described above, it should be understood that the above is only
For specific embodiments of the present invention, it is not intended to restrict the invention, all any modifications made in spirit of the invention,
Supplement or similar fashion substitution etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of in-situ preparation method of sulfonic polymeric object electrolyte, it is characterised in that the following steps are included: 1) by polymer
It is dissolved in the polymer solution for forming that mass fraction is 5%~30% in solvent, the silane coupling agent for containing-SH base is added, is mixed
The bubble and film forming that system is removed after closing uniformly, obtain the polymer film with a thickness of 1-100 μm；Wherein the polymer is poly- first
At least one of base methyl acrylate, polyacrylonitrile, Kynoar ,-six propylene copolymer of Kynoar, the solvent
It is the good solvent of the polymer；2) obtained polymer film is immersed into 0.3~6h in oxidizing agent solution, makes-SH base oxygen in film
Turn to-SO3H base, while silane coupling agent hydrolysis generates SiO2, to be contained-SO3The SiO of H base2Inorganic whisker is poly-
Compound film is immersed in the acid solution of 0.01~12M after being eluted by deionized water and is further protonated, then eluted with deionized water
And boil and remove remaining acid, obtain sulfonic polymeric object film；3) sulfonic polymeric object film is immersed concentration is 0.01-5mol
L-1Lithium exchange liquid in carry out lithium exchange, is then rinsed and is boiled with deionized water, drying, obtain the sulphur containing Sulfonic Lithium
Acid-based polymer electrolyte.
2. the in-situ preparation method of sulfonic polymeric object electrolyte according to claim 1, it is characterised in that: in step 1),
It further include the inorganic lewis acid that 0.01-5% mass fraction is added into the polymer solution；The inorganic lewis acid choosing
From at least one of nanoscale aluminum oxide, silica, calcium oxide, magnesia, lithium fluoride, titanium dioxide.
3. the in-situ preparation method of sulfonic polymeric object electrolyte according to claim 1, it is characterised in that: in step 1),
The film forming is then mixed solution is dried 0.5~50h in being cast or scratching in substrate under 40~100 DEG C of vacuum conditions
And stripping group bottom forms the polymer film, wherein the substrate is glass plate or polyfluortetraethylene plate.
4. the in-situ preparation method of sulfonic polymeric object electrolyte according to claim 1, it is characterised in that: in step 1),
The film forming is that mixed solution is obtained non-woven polymers film by spinning.
5. the in-situ preparation method of sulfonic polymeric object electrolyte according to claim 1, it is characterised in that: in step 1),
The good solvent of the polymer is N-Methyl pyrrolidone or N,N-dimethylformamide.
6. the in-situ preparation method of sulfonic polymeric object electrolyte according to claim 1, it is characterised in that: in step 2),
The oxidizing agent solution is hydrogen peroxide, nitric acid, potassium permanganate, potassium bichromate or hypochlorite solution.
7. the in-situ preparation method of sulfonic polymeric object electrolyte according to claim 1, it is characterised in that: in step 2),
The acid solution is at least one of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid.
8. the in-situ preparation method of sulfonic polymeric object electrolyte according to claim 1, it is characterised in that: in step 3),
The lithium exchange liquid is molten for the water or ethyl alcohol of at least one of lithium acetate, lithium nitrate, lithium sulfate, lithium metasilicate, lithium hydroxide
Liquid.
9. the sulfonic acid of the in-situ preparation method preparation of sulfonic polymeric object electrolyte as described in any one of claim 1~8
Base polymer electrolyte.
10. application of the sulfonic polymeric object electrolyte in electrochmical power source system described in claim 9, the electrochmical power source include
Lithium ion battery.
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| CN110994046B (en) * | 2019-12-04 | 2022-06-24 | 中南大学 | Mixed electrolyte of water-based ion battery |
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| CN111477957B (en) * | 2020-04-22 | 2021-04-16 | 浙江大学 | Lithium metal battery electrolyte containing composite additive and preparation method thereof |
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| US5161048A (en) * | 1990-12-26 | 1992-11-03 | Ppg Industries, Inc. | Electrochromic window with metal grid counter electrode and acidic polyelectrolyte |
| KR20030075101A (en) * | 2002-03-16 | 2003-09-22 | 한국과학기술연구원 | Gel type polymer electrolyte including leveling agent, lithium metal polymer battery with it, and fabrication method thereof |
| CN101218281A (en) * | 2005-06-09 | 2008-07-09 | 东洋纺织株式会社 | Sulfonic acid group-containing polymer, method for producing same, resin composition containing such sulfonic acid group-containing polymer, polymer electrolyte membrane, polymer electrolyte membrane/ |
| JP2010202866A (en) * | 2009-02-09 | 2010-09-16 | Tokyo Institute Of Technology | Sulfonated polymer and proton conductive membrane using the same |
| CN105899584A (en) * | 2014-01-15 | 2016-08-24 | 庄臣及庄臣视力保护公司 | Polymers comprising sulfonic acid groups |
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