阅读说明：本技术 一种碱性氧化还原液流电池用离子交换膜的制备方法 (A kind of preparation method of alkaline oxygenated reduction flow battery amberplex ) 是由 贾传坤 韩杰 丁美 于 2019-08-05 设计创作，主要内容包括：本发明涉及碱性氧化还原液流电池储能领域,具体是一种碱性氧化还原液流电池用离子交换膜的制备方法,主要用于解决现阶段碱性液流电池中Nafion隔膜价格昂贵的问题,从而大幅度降低液流电池成本。以铁氰化物(如：Na<Sub>3</Sub>[Fe(CN)<Sub>6</Sub>]、K<Sub>3</Sub>[Fe(CN)<Sub>6</Sub>]、(NH<Sub>4</Sub>)<Sub>3</Sub>[Fe(CN)<Sub>6</Sub>]等)的碱性水溶液作为正极电解液,以强碱溶液(如：KOH、NaOH等)作为负极电解液；选用石墨毡、碳毡作为正极材料,锌板作为负极材料；采用离子化后的磺化聚醚醚酮(SPEEK)隔膜作为离子交换膜组装电池。从而,获得具有低成本和高性能的碱性氧化还原液流电池体系。本发明中的液流电池体系具有开路电压高、成本低、效率高、循环稳定性好、安全可靠等优点,具有广阔的应用前景。(The present invention relates to alkaline oxygenated reduction flow battery energy storage fields, the preparation method of specifically a kind of alkaline oxygenated reduction flow battery amberplex, it is mainly used for solving the problems, such as in alkaline flow battery at this stage that Nafion diaphragm is expensive, so that flow battery cost be greatly lowered.(such as: Na with the iron cyanide 3 [Fe(CN) 6 ]、K 3 [Fe(CN) 6 ]、(NH 4 ) 3 [Fe(CN) 6 ] etc.) and alkaline aqueous solution as anode electrolyte, using strong base solution (such as: KOH, NaOH) as electrolyte liquid；Select graphite felt, carbon felt as positive electrode, zine plate is as negative electrode material；Using sulfonated polyether-ether-ketone (SPEEK) diaphragm after ionization as amberplex assembled battery.To which obtaining has low cost and high performance alkaline oxygenated reduction flow battery system.Flow battery system in the present invention has many advantages, such as high open-circuit voltage, at low cost, high-efficient, good cycling stability, safe and reliable, has broad application prospects.)

1. a kind of preparation method of alkaline oxygenated reduction flow battery amberplex, which is characterized in that include the following steps And process conditions:

(1) strong base solution is prepared in beaker with deionized water；

(2) it the preparation of sulfonated polyether-ether-ketone: weighs polyether-ether-ketone powder and is placed in the concentrated sulfuric acid that concentration is 98wt%, 30~80 Under DEG C constant temperature, it is stirred to react 0.5~6h；

(3) solution of step (2) after reaction is poured into deionized water and is stirred with glass bar, be frozen into it cotton-shaped, It is washed with deionized to the range of pH=5~7 again；Then, in 20~100 DEG C of 10~30h of freeze-day with constant temperature, dry wadding is obtained Shape sulfonated polyether-ether-ketone；

(4) the cotton-shaped sulfonated polyether-ether-ketone that step (3) obtains is shredded and is scattered in organic solvent, it is molten to be made into sulfonated polyether-ether-ketone Liquid；

(5) the resulting sulfonated polyether-ether-ketone solution of step (4) is poured into in reeded glass plate, is carried out at freeze-day with constant temperature Reason obtains sulfonated polyether-ether-ketone diaphragm；

(6) step (5) is obtained into sulfonated polyether-ether-ketone diaphragm and is placed in step (1) prepared strong base solution, carry out water bath with thermostatic control Ionization is taken out beaker, after being cooled to room temperature, is rinsed with deionized water to neutrality, then impregnate in deionized water, as battery Amberplex it is spare；

(7) using graphite felt or carbon felt as the anode of battery, using zine plate as the cathode of battery；

(8) it takes in above-mentioned steps (1) prepared strong base solution, the electrolyte liquid as battery；

(9) iron cyanide is taken to be dissolved in above-mentioned steps (1) prepared strong base solution, the alkalinity for being made into the iron cyanide is water-soluble Liquid, the anode electrolyte as battery；

(10) step (6), (7), (8), (9) resulting critical material are assembled into alkaline oxygenated reduction flow battery system, used Battery test system is tested.

2. the preparation method of alkaline oxygenated reduction flow battery amberplex according to claim 1, feature exist In in step (1), strong base solution is KOH or NaOH aqueous solution, and molar concentration is 1~8M.

3. the preparation method of alkaline oxygenated reduction flow battery amberplex according to claim 1, feature exist In in step (2), mixing speed is 100~1200r/min, and the mass volume ratio of polyether-ether-ketone powder and the concentrated sulfuric acid is 1/60 ~1/10g/mL, the partial size of polyether-ether-ketone powder are 50~60 μm.

4. the preparation method of alkaline oxygenated reduction flow battery amberplex according to claim 1, feature exist In in step (3), the speed that solution is toppled over is 100~200mL/min.

5. the preparation method of alkaline oxygenated reduction flow battery amberplex according to claim 1, feature exist In in step (4), the mass volume ratio of cotton-shaped sulfonated polyether-ether-ketone and organic solvent is 1/50~1/10g/mL, organic solvent For one of n,N-Dimethylformamide, dimethyl sulfoxide, n,N-dimethylacetamide, N-Methyl pyrrolidone.

6. the preparation method of alkaline oxygenated reduction flow battery amberplex according to claim 1, feature exist In, in step (5), drying temperature be 30~70 DEG C, drying time be 12~for 24 hours, the sulfonation degree of sulfonated polyether-ether-ketone diaphragm is 30~70%.

7. the preparation method of alkaline oxygenated reduction flow battery amberplex according to claim 1, feature exist In, in step (6), sulfonated polyether-ether-ketone diaphragm water-bath ionization processing temperature be 30~100 DEG C, processing the time be 0.5~ 1.5h。

8. the preparation method of alkaline oxygenated reduction flow battery amberplex according to claim 1, feature exist In in step (8), electrolyte liquid molar concentration is 2~6 M.

9. the preparation method of alkaline oxygenated reduction flow battery amberplex according to claim 1, feature exist In in step (9), the active material of anode electrolyte is the hexacyanoferrate to appraise at the current rate, and prepared iron cyanide alkalinity is water-soluble Liquid molar concentration is 0.1~1.0M, iron cyanide Na₃[Fe(CN)₆]、K₃[Fe(CN)₆] or (NH₄)₃[Fe(CN)₆]。

Technical field:

The present invention relates to alkaline oxygenated reduction flow battery energy storage field, specifically a kind of alkaline oxygenated reduction flow battery With the preparation method of amberplex.

Background technique:

The development and utilization of clean energy resource (such as: wind energy, solar energy) is the inexorable trend of future source of energy development, but these The energy is susceptible to the influence of weather, can not continuous and effective be connected to the grid.Therefore, it develops a kind of economical, efficient, stable big Scale energy storage technology simultaneously effectively stores various new energy most important.Because of its flexible structure, have extended cycle life, safety The advantages that reliable, flow battery become one of the energy storage candidate of most prospect.All-vanadium flow battery has excellent electrochemistry Energy.But in recent years, rising suddenly and sharply for navajoite resource price restricts vanadium with the expensive of DuPont Corporation Nafion series diaphragm cost The commercialized development of battery.Therefore, it is highly desirable to develop a kind of novel inexpensive flow battery system.

Positive and negative anodes electrolyte can be separated effectively as one of big critical material of flow battery three and can allow spy by diaphragm The closed circuit that fixed ion passes through composition inside battery.Ideal diaphragm material should have excellent ion selectivity, height Proton conductivity, good chemical stability and mechanical stability.Currently, commercial amberplex is mostly Dupont The Nafion series of company's production, costly, ion selectivity is poor for price, and cross contamination is serious.Sulfonated polyether-ether-ketone (SPEEK) diaphragm has many advantages, such as that proton conductivity is high, ion selectivity is good, at low cost, preparation process is simple, is ground by many The favor for the person of studying carefully.China's zinc-iron reserves are extremely abundant, can be effectively reduced the cost of flow battery.Therefore, using it is a kind of it is low at This SPEEK diaphragm substitutes expensive Nafion diaphragm, assembles Alkaline Zinc iron liquid galvanic battery.

Summary of the invention:

For overcome the deficiencies in the prior art, the constraint of amberplex is broken through, it is an object of the invention to propose one kind The preparation method of alkaline oxygenated reduction flow battery amberplex solves alkali at this stage using the SPEEK diaphragm of low cost The expensive problem of nafion film in property flow battery.This alkaline flow battery system have open-circuit voltage it is high, it is high-efficient, at The advantages that this is low, good cycling stability, can be greatly lowered the cost of alkaline flow battery, to instructing inexpensive flow battery Exploitation is of great significance.

Technical scheme is as follows:

A kind of preparation method of alkaline oxygenated reduction flow battery amberplex, includes the following steps and technique item Part:

(1) strong base solution is prepared in beaker with deionized water；

(2) it the preparation of sulfonated polyether-ether-ketone: weighs polyether-ether-ketone powder and is placed in the concentrated sulfuric acid that concentration is 98wt%, 30 Under~80 DEG C of constant temperatures, it is stirred to react 0.5~6h；

(3) solution of step (2) after reaction is poured into deionized water and is stirred with glass bar, it is made to be frozen into wadding Shape, then be washed with deionized to the range of pH=5~7；Then, in 20~100 DEG C of 10~30h of freeze-day with constant temperature, drying is obtained Cotton-shaped sulfonated polyether-ether-ketone；

(4) the cotton-shaped sulfonated polyether-ether-ketone that step (3) obtains is shredded and is scattered in organic solvent, be made into sulfonated polyether ether Ketone solution；

(5) the resulting sulfonated polyether-ether-ketone solution of step (4) is poured into in reeded glass plate, it is dry carries out constant temperature Dry processing obtains sulfonated polyether-ether-ketone diaphragm；

(6) step (5) is obtained into sulfonated polyether-ether-ketone diaphragm and is placed in step (1) prepared strong base solution, carry out constant temperature Water-bath ionization, take out beaker, after being cooled to room temperature, rinsed with deionized water to neutrality, then impregnate in deionized water, as The amberplex of battery is spare；

(7) using graphite felt or carbon felt as the anode of battery, using zine plate as the cathode of battery；

(8) it takes in above-mentioned steps (1) prepared strong base solution, the electrolyte liquid as battery；

(9) it takes the iron cyanide to be dissolved in above-mentioned steps (1) prepared strong base solution, is made into the alkaline water of the iron cyanide Solution, the anode electrolyte as battery；

(10) step (6), (7), (8), (9) resulting critical material are assembled into alkaline oxygenated reduction flow battery body System, is tested with battery test system.

The preparation method of the alkaline oxygenated reduction flow battery amberplex, in step (1), strong base solution is KOH or NaOH aqueous solution, molar concentration are 1~8M.

The preparation method of the alkaline oxygenated reduction flow battery amberplex, in step (2), mixing speed is The mass volume ratio of 100~1200r/min, polyether-ether-ketone powder and the concentrated sulfuric acid is 1/60~1/10g/mL, polyether-ether-ketone powder Partial size be 50~60 μm.

The preparation method of the alkaline oxygenated reduction flow battery amberplex, in step (3), what solution was toppled over Speed is 100~200mL/min.

The preparation method of the alkaline oxygenated reduction flow battery amberplex, in step (4), cotton-shaped sulfonation is poly- The mass volume ratio of ether ether ketone and organic solvent is 1/50~1/10g/mL, and organic solvent is n,N-Dimethylformamide, diformazan One of base sulfoxide, n,N-dimethylacetamide, N-Methyl pyrrolidone.

The preparation method of the alkaline oxygenated reduction flow battery amberplex, in step (5), drying temperature is 30~70 DEG C, drying time is 12~for 24 hours, the sulfonation degree of sulfonated polyether-ether-ketone diaphragm is 30~70%.

The preparation method of the alkaline oxygenated reduction flow battery amberplex, in step (6), sulfonated polyether ether The temperature of ketone diaphragm water-bath ionization processing is 30~100 DEG C, and the processing time is 0.5~1.5h.

The preparation method of the alkaline oxygenated reduction flow battery amberplex, in step (8), electrolyte liquid Molar concentration is 2~6M.

The preparation method of the alkaline oxygenated reduction flow battery amberplex, in step (9), anode electrolyte Active material be the hexacyanoferrate to appraise at the current rate, prepared iron cyanide alkaline aqueous solution molar concentration be 0.1~1.0M, iron Cyanide is Na₃[Fe(CN)₆]、K₃[Fe(CN)₆] or (NH₄)₃[Fe(CN)₆]。

Design philosophy of the invention is:

Compared with perfluorosulfonic acid proton exchange film, SPEEK diaphragm has excellent ion selectivity, high proton conductive Many advantages, such as rate, lower cost, relatively good mechanical performance and chemical stability.For monomer, this collaboration is had no The mechanism of action.The present invention prepares a kind of inexpensive, high proton conductivity SPEEK diaphragm by solution-casting method, for replacing It is applied to the flow battery of the alkaline potassium ferricyanide-zine plate system for expensive Nafion diaphragm.SPEEK diaphragm through water-bath from After sub-ization processing, SPEEK-H⁺Diaphragm is transformed into SPEEK-Na⁺Type diaphragm, while capable of guaranteeing the normal transmission of specific ion The effective cross contamination for preventing active ion, effectively avoids the self discharge of battery, the coulombic efficiency of battery is greatly improved.It is such Diaphragm has lower cost, and preferable ionic conductivity can be effectively reduced the internal resistance of battery system, improves cell voltage effect Rate.Higher coulombic efficiency and voltage efficiency make battery have a higher energy efficiency.Under alkaline condition, the battery Possess higher open-circuit voltage, enabling it to metric density can compare favourably with vanadium cell.Therefore, SPEEK diaphragm is expected to substitute valence The commercial Nafion diaphragm of lattice valuableness.The low cost of the electrolyte economic advantages of the alkaline system itself upper diaphragm in addition, favorably In the research and development for instructing inexpensive flow battery, it is pushed further into the process of industrialization of flow battery field energy storage.

Compared with prior art, the present invention have the advantages that it is following significant and the utility model has the advantages that

1, electrode material of the present invention using graphite felt, carbon felt as anode, electrode material of the zinc metal sheet as cathode.In cathode This structure used for the first time effectively avoids zinc metal sheet from directly contacting with diaphragm, and the zinc dendrite on zinc metal sheet of evading for innovating formula pacifies diaphragm The threat of full property.The flow battery system shows excellent cyclical stability.

2, the raw materials used in the present invention rich reserves, at low cost, safety and environmental protection, have broad application prospects.

3, whole preparation process of the present invention has equipment cost is low, low in raw material price easily obtains, operating process is simple etc. The advantages that practical is industrialized, the commercialization of low cost, the alkaline flow battery in high circulation service life is facilitated.

In short, the present invention proposes a kind of low cost, long circulation life, efficient aqueous alkaline flow battery system, adopt Use the electrode material of graphite felt, carbon felt as anode, electrode material of the zinc metal sheet as cathode；The alkaline aqueous solution of the iron cyanide is made For the anode electrolyte of battery, electrolyte liquid of the pure alkaline aqueous solution as battery；Using low cost SPEEK diaphragm at Function assembles a kind of alkaline flow battery of low cost.The material and raw material that the system uses are easy to get, at low cost, environmental protection Securely and reliably, it is suitble to extensive development, is conducive to develop a kind of low cost, long circulation life, efficient alkalinity flow battery.

Detailed description of the invention:

Fig. 1 is the molar concentration 0.1M iron cyanide-zine plate flow battery performance map.

Fig. 2 is the efficiency comparative of the molar concentration 0.5M iron cyanide-zine plate flow battery difference sulfonation degree SPEEK diaphragm Figure.

Fig. 3 is that the charge and discharge of the molar concentration 0.5M iron cyanide-zine plate flow battery difference sulfonation degree SPEEK diaphragm are bent Line comparison diagram.

Specific embodiment:

In the specific implementation process, the present invention is using graphite felt, carbon felt as flow battery positive electrode, zinc metal sheet or zine plate As flow battery negative electrode material.(such as: Na with the iron cyanide₃[Fe(CN)₆]、K₃[Fe(CN)₆]、(NH₄)₃[Fe(CN)₆] etc.) Alkaline aqueous solution adopted as anode electrolyte using the alkaline aqueous solution of highly basic (such as: KOH, NaOH) as electrolyte liquid Use sulfonated polyether-ether-ketone (SPEEK) diaphragm of ionized treated low cost, macroion selectivity as flow battery Amberplex, the sulfonation degree of amberplex are 40~70%, with a thickness of 70~90 microns.To which obtaining has low cost With the alkalinity redox flow batteries system of high battery performance.

In the following, being described further in conjunction with example to the present invention.