CN109659469A - A kind of flow battery ion-conductive membranes and its preparation and application - Google Patents
A kind of flow battery ion-conductive membranes and its preparation and application Download PDFInfo
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- CN109659469A CN109659469A CN201710940705.5A CN201710940705A CN109659469A CN 109659469 A CN109659469 A CN 109659469A CN 201710940705 A CN201710940705 A CN 201710940705A CN 109659469 A CN109659469 A CN 109659469A
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The present invention relates to a kind of flow battery ion-conductive membranes and its preparations and application, ion-conductive membranes matrix is prepared into using chloromethylation or bromomethylation organic polymer resin as raw material, or organic polymer resin is that mixed raw material is prepared into ion-conductive membranes matrix with chloromethylation or bromomethylation organic polymer resin, it first passes through hydrophilic agent and is grafted hydrophilic radical on ion-conductive membranes matrix, hydrophilic radical is quaternary ammonium group, then forms the ion-conductive membranes with cross-linked structure on above-mentioned film matrix by crosslinking agent；Wherein, the mass ratio of organic polymer resin and chloromethylation or bromomethylation macromolecule resin is 0-1 in matrix, and crosslinking agent is double amine groups.Such ion-conductive membranes has preparation process simple, the characteristics of ion transmission performance height, chemistry and good mechanical stability, therefore there is excellent ionic conduction performance, higher ion selectivity energy and good cyclical stability by the all-vanadium flow battery of the ion-conductive membranes assembling of above method preparation.
Description
Technical field
The present invention relates to a kind of flow battery ion-conductive membranes, in particular to a kind of ion of high ion-conductivity energy
Conductive membranes and its application in flow battery.
Background technique
It is increasingly serious due to energy crisis and environmental problem, it is therefore desirable to develop energy storage technology and improve renewable energy
Cleaning of using of the energy and sustainability are realized in the efficient utilization of (such as wind energy and solar energy).In numerous energy storage technologies
In, flow battery can satisfy the requirement with extensive energy stores for a long time, and have high conversion efficiency, system design spirit
It is living, storage capacity is high, addressing freely, can the advantages such as depth charge and discharge, safety and environmental protection, maintenance cost be low, and be concerned.Entirely
With high security, stability is good for vanadium flow battery (VFB), high-efficient, the service life long (average life span was in 15~20 years) and
Feature at low cost has become one of the one preferred technique that extensive energy storage technology promotes and applies.
Diaphragm is one of core building block of flow battery, mainly plays barrier positive and negative electrode electrolyte, prevents short
The effect on road and transmitting proton forming circuit.Flow battery diaphragm should have a good electronics barrier property, good chemistry and
Mechanical stability, good ionic conductivity and lower application cost.The diaphragm used in flow battery is mainly at present
Perfluorinated sulfonic acid class amberplex, the Nafion series membranes developed such as DuPont Corporation (DuPont Co.Ltd).Nafion
Series membranes mainly by stable C-F main chain and have-HSO3The branch of ion-exchange group is constituted, so that it is in flow battery
There is preferable stability and ionic conduction performance in, but it selects performance poor and at high cost, seriously makes
About its large-scale application in flow battery.Therefore urgently exploitation have good selectivity energy, superior chemical stability and
The flow battery film of ionic conductivity and low cost.
This team is dedicated to the research and development of porous ion conductive membranes for many years, by utilizing organic polymer resin
Steam phase inversion prepares a kind of spongy porous ion conductive membranes, since the film internal structure of this method preparation is not pass through
Logical spongy hole is mutually divided between Kong Yukong, therefore the perforated membrane of this structure needs to introduce ion-exchange group
It realizes ionic conduction between hole wall, passes through aperture screening transmitting ion in the inside in hole.This kind of perforated membrane due to introduce from
Sub- cation exchange groups cause the stability of film to reduce, and how to develop a kind of use suitable for flow battery has high stability, macroion
Conductibility, macroion selectivity ion-conductive membranes become the field research hotspot.
Summary of the invention
It is an object of the invention to develop it is a kind of with high stability, high ion-conductivity, macroion selectivity ion
Conductive membranes, and applied in flow battery application.
To achieve the above object, the present invention takes scheme as follows:
A kind of flow battery ion-conductive membranes, with one of macromolecule resin of chloromethylation or bromomethylation or
Two kinds the above are raw materials to be prepared into ion-conductive membranes matrix by steam phase transfer method or Solvent Evaporation Precipitation, passes through immersion
Graft reaction and immersion cross-linking reaction are grafted hydrophilic radical in ion-conductive membranes and form interior cross-linked structure, through acid
After change, the ion-conductive membranes of high ion-conductivity energy are prepared.
The organic polymer resin of the chloromethylation or bromomethylation is chloromethylation or bromomethylation polysulfones, chlorine
Methylation or bromomethylation polyimides and chloromethylation or bromomethylation polystyrene.
The hydrophilic radical of the grafting is the aliphatic amine (C of different chain lengthxH2x+1NH2, x is the integer of 2-20, preferably
Be n-butylamine when being n-propylamine or x=4 when x=3) or different fatty chain length N, N- dimethyl fatty amine [(CH3)2NH-
(CH2)xCH3, it is N, the N dimethyl positive last of the ten Heavenly stems when x is N, N dimethyl n hexylamine or x=10 when being the integer, preferably x=5 of 2-20
One or more of amine].Preferred hydrophilic agent can preferably construct micro phase separation structure.
It is described be used to prepare cross-linked structure and have ion exchange functionalities molecule be imidazoles, ethylenediamine, propane diamine, oneself
Diamines and p-phenylenediamine.It is preferred that imidazoles or/and p-phenylenediamine.The ion-conductive membranes with a thickness of 20-500 μm, hole
Rate is 0~80%.
The ion-conductive membranes with high ion-conductivity energy are formed different under different grafting and crosslinking time
Ion transmission network realizes that ion efficiently transmits in film.
The preparation method of above-mentioned ion-conductive membranes is prepared using following steps:
It (1) in organic solvent by chloromethylation or the dissolution of bromomethylation macromolecule resin, is 20~100 DEG C in temperature
Under 0.5~12h is sufficiently stirred uniform solution is made, wherein organic polymer resin and chloromethylation macromolecule resin concentration are 5
Between~70%；
(2) blend solution prepared by step (1) is poured on non-woven fabrics or dustless glass plate, is then placed in resin not
In the climatic chamber of good solvent, the organic solvent on surface is removed after 5~600 seconds, film thickness is 20~500 μm, constant temperature and humidity
Relative humidity is 50~100% in case, and temperature is 0~100 DEG C；
Or organic solvent is directly evaporated in 50~100 DEG C of thermal station, form a film after 12~48h, film thickness be 20~
500μm；
(3) hydrophilic agent is soluble in water, 0.5~5h is stirred, being configured to mass fraction is 10 water-soluble to saturation
Liquid；
(4) ion-conductive membranes prepared in step (2) are placed under the conditions of 0~100 DEG C prepared in step (3)
0.5~180h in solution, deionized water washing；
(5) crosslinking agent is soluble in water, 0.5~5h is stirred, is configured to mass fraction as 10 to saturation aqueous solution；
(6) ion-conductive membranes prepared in step (4) are placed under the conditions of 0~100 DEG C prepared in step (5)
0.5~180h in the solution of crosslinking agent；
(7) film prepared by step (6) is cleaned with deionized water, acidification in the acid solution of 0.1~3mol/L is added
It is stored in deionized water again.
The organic solvent is dimethyl sulfoxide (DMSO), DMAC N,N' dimethyl acetamide (DMAc), N- methyl pyrrolidone
(NMP), one of DMF (N, N '-dimethyl formamide) or two kinds or more；The poor solvent of resin is water (water), first
One of alcohol (methanol), ethyl alcohol (ethanol), propyl alcohol (propanol) or isopropanol (isopropanol) or two kinds
More than.
The ion-conductive membranes can be used in flow battery, and wherein flow battery includes all-vanadium flow battery, zinc/bromine liquid
Galvanic battery, sodium polysulfide/bromine redox flow cell, iron/chrome liquor galvanic battery, vanadium/bromine flow battery, zinc/iron liquid galvanic battery and zinc/iodine
The flow batteries such as flow battery.It is preferred that all-vanadium flow battery
Beneficial outcomes of the invention are as follows:
(1) by the ratio of regulation ion-conductive membranes hydrophilic radical and cross-linked structure, regulate and control the ruler of ion transmission channel
It is very little, realize the optimization to flow battery film ionic conductivity and selectivity.Meanwhile ion-conductive membranes can use Donnan row
Reprimand effect effectively inhibits the conduction in film of hydration vanadium ion, further increases the selectivity of ion-conductive membranes, so as to
It is enough to be preferably allowed to apply in flow battery system.
(2) ion-conductive membranes prepared by the present invention, the on the one hand flexible aliphatic chain in film surface grafting hydrophilic radical
The transmission that micro phase separation structure can be ion in film is formed between the main chain of rigidity more, broader transmission is provided lead to
Road improves conduction of the ion in film.On the other hand netted interior cross-linked structure is formed in film, can guarantee ion-conductive membranes
With good chemical stability.
(3) present invention impregnates the method for chemical reaction using two steps, prepares high ion-conductivity energy and high chemical stabilization
The ion-conductive membranes of property, method are simply amplified.
(4) crosslinking agent contains ion-exchange group, and hydrophily is stronger, can be effectively improved by introducing crosslinked structure
Interaction between polymer segment reduces effect of the solution to film, to effectively improve film in strong acid, strong oxidizing property
Under the conditions of stability.It can make ionic conduction film surface that there is lotus electropositive by quaternary ammoniated process, form Donnan effect,
There is certain repulsive interaction to the electropositive hydration vanadium ion in solution, the selection performance of film can be effectively improved.
(5) method of the present invention for improving ion-conductive membranes ionic conduction performance has preparation method simple, system
Standby ion-conductive membranes show preferable ionic conduction performance compared to known ion conductive membranes in all-vanadium flow battery,
Ion selectivity energy and chemical stability.
Detailed description of the invention
Fig. 1 is the working mechanism figure of ion-conductive membranes of the invention in all-vanadium flow battery
Fig. 2 is porous ion conductive membranes prepared by porous ion conductive membranes (a-a ') prepared by comparative example 2 and embodiment 1
The SEM of (b-d, b '-d ') schemes；
The cycle performance of the battery performance and embodiment (1-3) of Fig. 3 embodiment (1-3) and comparative example (1-2).
Specific embodiment
The following examples are not intended to limit the scope of the invention to further explanation of the invention.
Embodiment 1
10 grams of chloromethyl polysulphones, which are dissolved in 400 grams of DMAc, (wherein to be passed through1HNMR measures prepared chloromethyl polysulfones
Chloromethylation degree be 1.3), to stir 12h, form uniform polymer solution, stand de-bubble, scratch in dustless glass plate
On, it is put into 50 DEG C, 10 minutes in the climatic chamber of 100% relative humidity, is immersed in deionized water after removing the solvent on surface
Middle 12h.The porous ion conductive membranes of above-mentioned preparation are dipped into 40 DEG C, in 5% trimethylamine aqueous solution, takes out, goes after 5min
Ionized water cleaning, then the porous ion conductive membranes of above-mentioned grafting trimethylamine are dipped into 40 DEG C, in 10% imidazoles aqueous solution,
It is taken out after 72h, deionized water cleaning is immersed in the H of 3mol/L2SO412h in aqueous solution.
All-vanadium flow battery is assembled using porous ion conductive membranes prepared by the above method, wherein being bipolar with graphite plate
Plate；Porous active carbon felt is collector；The effective area of film is 48cm2；Positive and negative anodes electrolyte volume be 60mL, wherein vanadium from
The concentration of son is 1.50mol/L, H2SO4Concentration is 3mol/L.In charge-discharge test, current density 80mA/cm2, Fig. 3 can see
Out, coulombic efficiency 98.5%, voltage efficiency 90.1%, energy efficiency 88.7%, in 160mA/cm2Current density
Under, charge and discharge 1000 recycle, and energy efficiency maintains 80%.
Embodiment 2
Material characterization method and basement membrane preparation and characterizing method conduct the porous ion of above-mentioned preparation with embodiment 1
Film is dipped into 40 DEG C, in 5% pyridine solution, takes out after 5min, deionized water cleaning, then by the more of above-mentioned grafting pyridine
Ionic porogen conductive membranes are dipped into 40 DEG C, in 10% imidazoles aqueous solution, take out after 72h, and deionized water cleaning is immersed in 3mol/
The H of L2SO412h in aqueous solution.
Battery assembly and test condition are with embodiment 1, in charge-discharge test, current density 80mA/cm2, Fig. 3 can see
Out, coulombic efficiency 97.9%, voltage efficiency 91%, energy efficiency 89.1%, in 120mA/cm2Under current density,
Charge and discharge 1000 recycle, and energy efficiency maintains 81%.
Embodiment 3
4 grams of chloromethyl polysulphones (wherein pass through1The chloromethylation degree that HNMR measures prepared chloromethyl polysulfones is
1.2) it is dissolved in 16 grams of DMAc, stirs 12h, form uniform polymer solution, 0.5g piperidines is added, stirs into homogeneous solution
Afterwards, de-bubble is stood, is scratched on dustless glass plate, being put into evaporation solvent formation dense film in 50 DEG C of thermal station, (film thickness is about 32
μm), then the ion-conductive membranes of above-mentioned preparation are dipped into 40 DEG C, in 10% imidazoles aqueous solution, taken out after 72h, deionized water
Cleaning, is immersed in the H of 3mol/L2SO412h in aqueous solution.
Battery assembly and test condition are with embodiment 1, in charge-discharge test, current density 80mA/cm2, Fig. 3 can see
Out, coulombic efficiency 98.6%, voltage efficiency 91.2%, energy efficiency 89.9%, in 160mA/cm2Current density
Under, charge and discharge 1000 recycle, and energy efficiency maintains 82%.
Comparative example 1
By Nafion115 film according to the battery assembly and test method assembly battery in embodiment 1.It can from Fig. 3
Out, coulombic efficiency 93.2%, voltage efficiency 88.1%, energy efficiency 82.1%.
For the lotus positive electricity porous ion conductive membranes or dense film of preparation, due to be grafted hydrophilic radical increase from
Conductive performance of the son in film, while the selectivity of film is significantly enhanced by Donnan effect, so that the coulombic efficiency of film is tieed up
It holds 98% or so, voltage efficiency maintains 90% or so, and has no obvious change during 1000 charge and discharge cycles
Change.Prepared lotus positive electricity porous ion conductive membranes or dense film are superior in selectivity and ionic conduction performance identical
Compared with Nafion115 film under test condition.
Comparative example 2
The preparation method is the same as that of Example 1 for porous ion conductive membranes, and prepared porous ion conductive membranes are directly dipped into
It in 10% imidazoles aqueous solution, is taken out after 72h, deionized water cleaning is immersed in the H of 3mol/L2SO412h in aqueous solution.
Battery assembly and test condition are with embodiment 1, in charge-discharge test, current density 80mA/cm2, Fig. 3 can see
Out, coulombic efficiency 99.1%, voltage efficiency 86.3%, energy efficiency 85.5%, in 160mA/cm2Current density
Under, voltage efficiency 73.1%.Obtained ion-conductive membranes internal structure mechanism figure such as Fig. 1 left figure.
From Fig. 1 right figure, working mechanism of the ion-conductive membranes prepared by the present invention in all-vanadium flow battery be can be seen that, one
Aspect forms micro phase separation structure between the main chain of flexible aliphatic chain and rigidity in film surface grafting hydrophilic radical can
The transmission for being ion in film provides more, broader transmission channel, improves conduction of the ion in film, is conducive to battery and exists
Operation under high current density is conducive to the energy density for improving flow battery.On the other hand netted interior crosslinking is formed in film
Structure can guarantee that ion-conductive membranes have good chemical stability.
Claims (10)
1. a kind of flow battery ion-conductive membranes, it is characterised in that:
Ion-conductive membranes matrix or organic polymer are prepared into using chloromethylation or bromomethylation organic polymer resin as raw material
Resin and chloromethylation or bromomethylation organic polymer resin are that mixed raw material is prepared into ion-conductive membranes matrix, first pass through parent
Water-based reagent is grafted hydrophilic radical on ion-conductive membranes matrix, and hydrophilic radical is quaternary ammonium group, then passes through crosslinking agent
The ion-conductive membranes with cross-linked structure are formed on above-mentioned film matrix；Wherein, organic polymer resin and chloromethyl in matrix
Change or the mass ratio of bromomethylation macromolecule resin is 0-1, crosslinking agent is double amine groups.
2. ion-conductive membranes according to claim 1, it is characterised in that: the hydrophilic agent is CxH2x+1NH2Or
(CH3)2N-(CH2)xCH3One or more of, wherein integer of the x between 2-20.
3. ion-conductive membranes according to claim 1 or 2, it is characterised in that: the hydrophilic agent is n-propylamine, positive fourth
Amine, N, N dimethyl n-hexylamine, N, one or more of N dimethyl n-Decylamine.
4. ion-conductive membranes according to claim 1, it is characterised in that: it is described for crosslinking double amine groups for
Cross-linked structure and the crosslinking agent with ion exchanging function, crosslinking agent are imidazoles, ethylenediamine, propane diamine, hexamethylene diamine, p-phenylenediamine
One or more of.
5. ion-conductive membranes according to claim 4, it is characterised in that: the crosslinking agent is imidazoles or/and p-phenylenediamine.
6. ion-conductive membranes according to claim 1, it is characterised in that: the organic polymer resin is polysulfones, polyethers
One or more of sulfone, polyacrylonitrile, Kynoar, polystyrene, polyimides, polybenzimidazoles, chloromethyl
Organic polymer resin in change or bromomethylation organic polymer resin is one of polysulfones, polyimides, polystyrene
Or it is two or more, chloromethylation or bromomethylation degree are within the scope of 0.9-2.0.
7. ion-conductive membranes according to claim 1, it is characterised in that: the ion-conductive membranes are by steam inversion of phases
The perforated membrane of method preparation or the dense film of solvent volatilization precipitation method preparation, film matrix thickness is 20~500 μm, membrane porosity 0
~80%.
8. a kind of preparation method of ion-conductive membranes as claimed in claim 1 to 7, it is characterised in that: the ion-conductive membranes
It is prepared according to the following procedure,
1) at being in organic solvent by chloromethylation or the dissolution of bromomethylation macromolecule resin, 20~100 DEG C in temperature sufficiently
0.5~12h is stirred, wherein organic polymer resin is added or does not add, organic polymer resin and chloromethylation or bromomethyl
The mass ratio for changing macromolecule resin is 0-1, and concentration of polymer solution is 5~70%；
2) solution prepared by step (1) is poured on non-woven fabrics or dustless glass plate, is then placed in the perseverance of resin poor solvent
In constant temperature and humidity case, the solvent on surface is removed after 5~600 seconds, film thickness is 20~500 μm, and relative humidity is in climatic chamber
50~100%, temperature removes the organic solvent on surface after being 0~100 DEG C, 5~600 seconds, and film thickness is 20~500 μm；
Or organic solvent is directly evaporated in 50~100 DEG C of thermal station, it forms a film after 12~48h, film thickness is 20~500 μm；
3) hydrophilic agent is soluble in water, 0.5~5h is stirred, the aqueous solution that mass fraction is 10%- saturation is configured to；
4) ion-conductive membranes prepared in step (2) are placed under the conditions of 0~100 DEG C in solution prepared in step (3)
0.5~180h, deionized water washing；
5) crosslinking agent is soluble in water, 0.5~5h is stirred, the aqueous solution that mass fraction is 10%- saturation is configured to；
6) ion-conductive membranes prepared in step (4) are placed in crosslinking agent prepared in step (5) under the conditions of 0~100 DEG C
Solution in 0.5~180h；
7) film prepared by step (6) is cleaned with deionized water, acidification in the acid solution of 0.1~3mol/L is added and saves again
In deionized water.
9. preparation method according to claim 8, it is characterised in that:
The organic solvent is dimethyl sulfoxide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, N, N '-dimethyl formyl
One of amine or two kinds or more, the poor solvent of resin are one of water, methanol, ethyl alcohol, propyl alcohol or isopropanol or two kinds
More than；Acid solution is sulfuric acid, hydrochloric acid or aqueous solution of nitric acid.
10. a kind of application of the ion-conductive membranes as described in one of claim 1-7, it is characterised in that: the ion-conductive membranes can
For in flow battery, wherein flow battery to include all-vanadium flow battery, zinc/bromine flow battery, sodium polysulfide/bromine liquid stream electricity
Pond, iron/chrome liquor galvanic battery, vanadium/bromine flow battery, the flow batteries such as zinc/iron liquid galvanic battery and zinc/iodine solution galvanic battery.
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| CN110277529A (en) * | 2019-06-28 | 2019-09-24 | 新乡市中科科技有限公司 | A kind of high multiplying power lithium ion battery functional composite membrane and preparation method thereof |
| CN111040156A (en) * | 2019-11-28 | 2020-04-21 | 李南文 | Solvent-resistant and high-dimensional-stability cross-linked polyimide film |
| CN111200145A (en) * | 2018-11-16 | 2020-05-26 | 中国科学院大连化学物理研究所 | Ion conduction membrane with double ion channels and preparation and application thereof |
| CN112940321A (en) * | 2019-12-10 | 2021-06-11 | 中国科学院大连化学物理研究所 | Cross-linked composite membrane for flow battery and preparation and application thereof |
| WO2022140714A1 (en) * | 2020-12-23 | 2022-06-30 | Uop Llc | Electrolyte compositions for redox flow batteries |
| WO2023049700A1 (en) * | 2021-09-21 | 2023-03-30 | Uop Llc | Mitigation of solution cross-over using differential electrolyte formulations in redox flow battery systems |
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| WO2023049700A1 (en) * | 2021-09-21 | 2023-03-30 | Uop Llc | Mitigation of solution cross-over using differential electrolyte formulations in redox flow battery systems |
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