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CN103000970A - Al-H2O2 half fuel cell ion exchange membrane and its battery - Google Patents

Al-H2O2 half fuel cell ion exchange membrane and its battery Download PDF

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CN103000970A
CN103000970A CN2012104454625A CN201210445462A CN103000970A CN 103000970 A CN103000970 A CN 103000970A CN 2012104454625 A CN2012104454625 A CN 2012104454625A CN 201210445462 A CN201210445462 A CN 201210445462A CN 103000970 A CN103000970 A CN 103000970A
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anode
cathode
exchange membrane
casing
groove
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黄雯
王宇轩
林沛
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CETC 18 Research Institute
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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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

本发明涉及一种Al-H2O2半燃料电池用离子交换膜及其电池，其特点是：离子交换膜为AMA-40型阴离子交换膜；本发明电池包括位于所述阴离子交换膜两面的阳极部分和阴极部分。由于采用了AMA-40型阴离子交换膜，透过阴离子，电池放电中，通过OH-传导电荷，阴极产生的OH-能自动转移至阳极，避免了OH-在阴极电解液中的过度积累，降低了H2O2分解速率，提高了H2O2利用率，阳极还得到了OH-的补充，从而减少阳极电解液中NaOH的用量，降低了电解质的添加量，提高了电池的比能量，还阻挡了阳离子通过，有效阻断了Al3+向阴极的迁移，防止了Al(OH)3沉淀的形成，提高了电池性能和离子交换膜的使用寿命。

Figure 201210445462

The present invention relates to an ion exchange membrane for an Al-H 2 O 2 semi-fuel cell and a battery thereof, which is characterized in that: the ion exchange membrane is an AMA-40 type anion exchange membrane; the battery of the present invention includes Anode part and cathode part. Due to the adoption of the AMA-40 type anion exchange membrane, through the anion, during the discharge of the battery, the charge is conducted through OH - , and the OH - generated by the cathode can be automatically transferred to the anode, avoiding the excessive accumulation of OH - in the catholyte, reducing the The decomposition rate of H 2 O 2 is improved, the utilization rate of H 2 O 2 is improved, and the anode is also supplemented by OH - , thereby reducing the amount of NaOH in the anolyte, reducing the amount of electrolyte added, and improving the specific energy of the battery. It also blocks the passage of cations, effectively blocks the migration of Al 3+ to the cathode, prevents the formation of Al(OH) 3 precipitates, and improves the performance of the battery and the service life of the ion exchange membrane.

Figure 201210445462

Description

Al-H 2O 2Semi-fuel cell amberplex and battery thereof
Technical field
The invention belongs to technical field of chemical power, particularly relate to a kind of high energy low consumption Al-H 2O 2Semi-fuel cell.
Background technology
Al-H 2O 2Semi-fuel cell maximum system energy density is high, is particularly suitable for long-time discharge.At Al-H 2O 2In the semi-fuel cell, because H 2O 2Catholyte contacts with positive plate direct chemical reaction can occur, this side reaction can not produce foreign current, but can consume the active material more than 50%, reduce the output energy of battery, therefore usually adopt and such as the Nafion cation-exchange membrane cathode and anode is kept apart.Al-H 2O 2Main chemical reactions equation as shown in table 1 occurs during battery discharge, and along with the carrying out of exoelectrical reaction, the negative electrode negative electrical charge is on the increase, because the Nafion cation-exchange membrane is that selectivity sees through Na +, stop simultaneously anion to see through, so Na +Be transferred to the catholyte from anolyte, realize the charge conservation of battery; Usually can there be following three drawbacks when adopting cation-exchange membrane: at first, because H 2O 2Electrode one side will constantly generate OH -, OH -Continuous accumulation the pH value of solution is raise, and under alkali condition, along with the increase of pH value, H 2O 2Decompose and produce O 2Speed can obviously increase, therefore cause H 2O 2Utilance significantly reduces.Secondly, because cation-exchange membrane can't be blocked the Al in the anode part 3+To the diffusion of negative electrode, Al 3+Understand the OH with negative electrode -Form Al (OH) 3Colloidal precipitation, the catalytic performance of reduction cathod catalyst affects the regular picture reaction of negative electrode, and the generation of precipitation also can reduce ionic conductivity and the useful life of amberplex greatly.At last, for 6e -Direct oxidation is as shown in table 1,2molAl 3+Need 8mol Na +Come conduct charges, NaOH concentration must be Al in solution 3+More than 4 times, could satisfy the needs of battery discharge, higher material consumption has reduced the high-energy-density advantage of battery.
Table 1Al-H 2O 2The main chemical reactions equation of semi-fuel cell
Negative electrode: 3H 2O 2 +6e --→6OH -
Anode: 2Al+8OH --→2AlO 2 -+4H 2O+6e -
Cell reaction: 2Al+3H 2O 2+2OH --→2AlO 2 -+4H 2O
Summary of the invention
The present invention provides H for solving the technical problem that exists in the background technology 2O 2A kind of Al-H that utilance is high, raw materials consumption is few, produce without the colloid sediment 2O 2The semi-fuel cell amberplex.
The technical scheme that the present invention takes is:
Al-H 2O 2The semi-fuel cell amberplex is characterized in: described amberplex is AMA-40 type anion-exchange membrane.
Adopt the Al-H of AMA-40 type anion exchange film preparation 2O 2Semi-fuel cell is characterized in: be positioned at the sealing of two sides, the anion-exchange membrane left and right sides and be fixed with anode part and cathode portion; Anode part comprises the anode casing that is shaped with an anode groove on the one side, and the anode groove floor is shaped with two holes, is respectively the outlet of anolyte import and anolyte, is anode current collector plate, metallic anode plate and anode flow channel from left to right in the anode casing; Cathode portion comprises the cathode shell that is shaped with a cathode slots on the one side, and the cathode slots bottom surface is shaped with two holes, is respectively the outlet of catholyte import and catholyte, and cathode shell is interior to be cathode collector plate, catalytic cathode and cathode flow channels from right-to-left.
The present invention can also adopt following technical scheme:
Described anode flow channel is that Vertical Uniform of metallic anode plate is pasted cylindrical phenolic resins barrier film grain, is formed by the gap between the barrier film grain; Described cathode flow channels is that the nickel foam substrate one side of catalytic cathode evenly is suppressed with groove.
Be shaped with a cannelure on the corresponding surface of described anode casing and amberplex as the anode seal groove, be shaped with a cannelure on the contact-making surface of cathode shell and amberplex as the negative electrode seal groove, the shape of anode seal groove and negative electrode seal groove is identical, be of a size of scaled down; The seal groove of anode casing is built-in with the anode seal circle; The seal groove of cathode shell is built-in with the negative electrode sealing ring.
Described anode is aluminium alloy.
Described anode casing and cathode shell material are thickness greater than the 3240 epoxy phenolics plates of 10mm; The anode part on described anion-exchange membrane and two sides, the left and right sides and cathode portion are loaded into one by the screw bolt and nut sealing.
Advantage and good effect that the present invention has are:
1, the present invention is at Al-H 2O 2In the semi-fuel cell since adopted AMA-40 type anion-exchange membrane as amberplex because, selectivity has seen through anion, battery passes through OH in discharge process -Conduct charges, the OH that negative electrode produces -Can be automatically transferred to anode, not only avoid OH -Excessive accumulation in catholyte has reduced H 2O 2Decomposition rate, Effective Raise H 2O 2Utilance, and anode has also obtained OH -Replenish, thereby reduce the consumption of NaOH in the anolyte, reduced electrolytical addition, improved the specific energy of battery.
2, the present invention has stopped that also cation passes through owing to adopt AMA-40 type anion-exchange membrane, has effectively blocked Al 3+To the migration of negative electrode, prevented Al (OH) 3The formation of precipitation, the useful life of having improved battery performance and amberplex.
Description of drawings
Fig. 1 is the Al-H that adopts the present invention's preparation 2O 2The semi-fuel cell structural representation;
Among the figure, 1-negative electrode sealing ring; The 2-cathode shell; The 3-nut; The 4-bolt; The 5-cathode slots; The outlet of 6-catholyte; 7-cathode collector plate; The 8-catalytic cathode; The 9-cathode flow channels; The import of 10-catholyte; The 11-anion-exchange membrane; The import of 12-anolyte; 13-anode current collector plate; The 14-positive plate; The 15-anode flow channel; The outlet of 16-anolyte; 17-anode groove; The 18-anode casing; 19-anode seal circle; The 20-cathode portion; The 21-anode part.
Embodiment
For further understanding summary of the invention of the present invention, Characteristic, hereby exemplify following examples, and cooperate accompanying drawing to be described in detail as follows:
Al-H 2O 2The semi-fuel cell amberplex, its innovative point is: described amberplex is AMA-40 type anion-exchange membrane.
Adopt the Al-H of AMA-40 type anion exchange film preparation 2O 2Semi-fuel cell, its innovative point is: be positioned at the sealing of two sides, the anion-exchange membrane left and right sides and be fixed with anode part and cathode portion; Anode part comprises the anode casing that is shaped with an anode groove on the one side, and the anode groove floor is shaped with two holes, is respectively the outlet of anolyte import and anolyte, is anode current collector plate, metallic anode plate and anode flow channel from left to right in the anode casing; Cathode portion comprises the cathode shell that is shaped with a cathode slots on the one side, and the cathode slots bottom surface is shaped with two holes, is respectively the outlet of catholyte import and catholyte, and cathode shell is interior to be cathode collector plate, catalytic cathode and cathode flow channels from right-to-left.
Embodiment
Adopt AMA-40 type anion exchange film preparation Al-H of the present invention 2O 2The process of semi-fuel cell: as shown in Figure 1:
At thickness greater than the square 3240 epoxy phenolics plates of 10mm as the material of making anode part 21 and cathode portion 20, anode part processes an anode groove 17 as anode casing 18 for the one side centre, the anode groove floor is shaped with two holes, respectively as anolyte import 12 and anolyte outlet 16, anode casing respectively processes a through hole near four jiaos of places, make a cannelure as the anode seal groove on the unsealed end face of anode casing, place anode seal circle 19 in the anode seal groove, the anode current collector plate 13 of making for the nickel plate from left to right in the anode groove, the positive plate 14 that aluminium alloy is made, the another side Vertical Uniform of positive plate is pasted cylindrical phenolic resins barrier film grain, and the gap between the barrier film grain forms anode flow channel 15; Cathode portion processes a cathode slots corresponding with the anode groove 5 as cathode shell 2 for the one side centre, the cathode slots bottom surface is shaped with two holes, respectively as catholyte import 10 and catholyte outlet 6, cathode shell respectively processes through holes corresponding with the through hole at the close four jiaos of places of anode casing near four jiaos of places, make an annular seal groove as the negative electrode seal groove on the unsealed end face of cathode shell, the size of negative electrode seal groove is amplified a circle than the size equal proportion of anode seal groove, when making two housing seals fixedly, form two parallel annular seal grooves, place negative electrode sealing ring 1 in the negative electrode seal groove, cathode slots is interior to be the cathode collector plate 7 that the nickel plate is made from right-to-left, catalytic cathode 8 and cathode flow channels 9, wherein, with the substrate of porous nickel mesh as catalytic cathode, substrate is positioned at cathode collector plate one side, substrate simultaneously plates layer of gold as reducing catalyst, evenly suppresses groove as cathode flow channels at the substrate another side; Then the not sealing end face correspondence with anode casing and cathode shell is attached to AMA-40 type anion-exchange membrane 11 two sides, pass the through hole at anode casing and four jiaos of places of cathode shell with bolt 4, with nut 3 fastening bolts, anode casing and cathode shell sealing are fixed into one; Form high energy low consumption Al-H of the present invention 2O 2Semi-fuel cell.When battery operated, by peristaltic pump with 3.4%NaCl+2.5M KOH+10g/LNa 2SnO 3Anolyte flows into from the anolyte import, flow out from the anolyte outlet to circulate, by another peristaltic pump with 3.4%NaCl+0.5M H 2O 2Catholyte flows into from the catholyte import, flows out from the catholyte outlet to circulate, to Al-H of the present invention 2O 2Semi-fuel cell discharges and tested in 4 hours, and reaction temperature is room temperature, and flow is 25ml/min, H 2O 2Utilance can reach 78.6%.
Comparative Examples
Preparation process is identical with embodiment, and difference is that amberplex adopts cation-exchange membrane Nafion115; Because OH in the catholyte -Constantly accumulation, the pH value constantly raises, and makes H 2O 2Decomposition rate increases; Discharge and test H after 4 hours 2O 2Utilance only is 27.2%.
From above result as can be known: because the present invention adopts anion-exchange membrane as the barrier film between the anode and cathode, can selectivity see through OH -, OH -Directly conduct to anode by negative electrode, avoided OH -Accumulation at negative electrode has reduced H 2O 2Be decomposed into O 2Speed, so H 2O 2Utilance is increased to 78.6%.And adopted the Al-H of Nafion cation-exchange membrane in the past 2O 2Battery, H 2O 2Utilance only is 27.2%.Simultaneously, adopt anion-exchange membrane, stopped that also cation sees through, effectively blocked Al 3+To the migration of negative electrode, prevented Al (OH) 3The formation of precipitation can also improve useful life and the specific energy of battery.
Although the above is described the preferred embodiments of the present invention by reference to the accompanying drawings; but the present invention is not limited to above-mentioned embodiment; above-mentioned embodiment only is schematic; be not restrictive; those of ordinary skill in the art is under enlightenment of the present invention; not breaking away from the scope situation that aim of the present invention and claim protect, can also make a lot of forms, these all belong within protection scope of the present invention.

Claims (6)

1.Al-H2O2半燃料电池用离子交换膜，其特征在于：所述的离子交换膜为AMA-40型阴离子交换膜。1. Al-H 2 O 2 ion-exchange membrane for semi-fuel cells, characterized in that: the ion-exchange membrane is an AMA-40 type anion-exchange membrane. 2.采用权利要求1制备的Al-H2O2半燃料电池，其特征在于：位于阴离子交换膜左右两面密封固装有阳极部分和阴极部分；阳极部分包括一面上制有一阳极凹槽的阳极壳体，阳极凹槽底面制有两孔，分别为阳极电解液进口和阳极电解液出口，阳极壳体内自左至右为阳极集流板、金属阳极板和阳极流道；阴极部分包括一面上制有一阴极凹槽的阴极壳体，阴极凹槽底面制有两孔，分别为阴极电解液进口和阴极电解液出口，阴极壳体内自右至左为阴极集流板、催化阴极和阴极流道。2. The Al-H 2 O semi- fuel cell prepared according to claim 1 is characterized in that: the left and right sides of the anion exchange membrane are sealed and fixed with an anode part and a cathode part; the anode part includes an anode that is shaped on an anode groove on one side The casing has two holes on the bottom of the anode groove, which are the anolyte inlet and the anolyte outlet respectively. Inside the anode casing are the anode current collector plate, the metal anode plate and the anode flow channel from left to right; the cathode part includes one side A cathode casing with a cathode groove is made. There are two holes on the bottom of the cathode groove, which are respectively the catholyte inlet and the catholyte outlet. The cathode casing is the cathode collector plate, the catalytic cathode and the cathode flow channel from right to left. . 3.根据权利要求2所述的Al-H2O2半燃料电池用离子交换膜，其特征在于：所述阳极流道为金属阳极板一面垂直均匀粘贴圆柱形酚醛树脂隔膜粒，由隔膜粒之间的间隙形成；所述阴极流道为催化阴极的泡沫镍基底一面均匀压制有通槽。3. Al-H according to claim 2 O 2 ion exchange membranes for semi-fuel cells, characterized in that: the anode flow channel is a metal anode plate one side vertically evenly pasted cylindrical phenolic resin membrane grains, by the membrane grains The gap between them is formed; the cathode flow channel is uniformly pressed with through grooves on one side of the nickel foam substrate of the catalytic cathode. 4.根据权利要求2所述的Al-H2O2半燃料电池用离子交换膜，其特征在于：所述阳极壳体与离子交换膜的对应面上制有一环形槽作为阳极密封槽，阴极壳体与离子交换膜的接触面上制有一环形槽作为阴极密封槽，阳极密封槽与阴极密封槽的形状相同、尺寸为等比例缩小；阳极壳体的密封槽内置有阳极密封圈；阴极壳体的密封槽内置有阴极密封圈。4. Al-H according to claim 2 O 2 ion-exchange membranes for semi-fuel cells, characterized in that: an annular groove is formed on the corresponding surface of the anode casing and the ion-exchange membrane as the anode sealing groove, and the cathode An annular groove is formed on the contact surface of the casing and the ion exchange membrane as the cathode sealing groove. The shape of the anode sealing groove and the cathode sealing groove are the same, and the size is reduced in proportion; the sealing groove of the anode casing is built with an anode sealing ring; the cathode casing A cathode sealing ring is built in the sealing groove of the body. 5.根据权利要求2所述的Al-H2O2半燃料电池用离子交换膜，其特征在于：所述阳极为铝合金。5. The ion exchange membrane for Al-H 2 O 2 half fuel cells according to claim 2, characterized in that: the anode is aluminum alloy. 6.根据权利要求2所述的Al-H2O2半燃料电池用离子交换膜，其特征在于：所述阳极壳体和阴极壳体材料均为厚度大于10mm的3240环氧酚醛树脂板；所述阴离子交换膜及左右两面的阳极部分和阴极部分由螺栓和螺母密封固装成一体。6. The Al-H 2 O 2 ion exchange membrane for semi-fuel cells according to claim 2, characterized in that: the anode casing and cathode casing materials are 3240 epoxy phenolic resin plates with a thickness greater than 10mm; The anion exchange membrane, the anode part and the cathode part on the left and right sides are sealed and fixed together by bolts and nuts.
CN2012104454625A 2012-11-09 2012-11-09 Al-H2O2 half fuel cell ion exchange membrane and its battery Pending CN103000970A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103500865A (en) * 2013-10-18 2014-01-08 清华大学 Lithium-cathode semi-fuel cell component
CN105762396A (en) * 2016-03-03 2016-07-13 重庆大学 Flat-plate heat regeneration ammonium battery adopting foam metal electrode
CN106374129A (en) * 2016-11-09 2017-02-01 大连融科储能技术发展有限公司 A flow battery stack sealing structure
CN107004879A (en) * 2014-11-25 2017-08-01 庄信万丰燃料电池有限公司 Film seal assembly
CN110571437A (en) * 2018-05-16 2019-12-13 嘉兴市兆业新能源技术有限公司 An anode structure for a fuel cell

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CN101242017A (en) * 2007-12-28 2008-08-13 中国航天科技集团公司第六研究院第十一研究所 Half fuel cell
CN102332586A (en) * 2011-10-12 2012-01-25 中国电子科技集团公司第十八研究所 A semi-fuel cell for underwater power

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US20030124418A1 (en) * 2002-01-03 2003-07-03 Dow Eric G. Separated flow liquid catholyte aluminum hydrogen peroxide seawater semi fuel cell
CN101242017A (en) * 2007-12-28 2008-08-13 中国航天科技集团公司第六研究院第十一研究所 Half fuel cell
CN102332586A (en) * 2011-10-12 2012-01-25 中国电子科技集团公司第十八研究所 A semi-fuel cell for underwater power

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103500865A (en) * 2013-10-18 2014-01-08 清华大学 Lithium-cathode semi-fuel cell component
CN103500865B (en) * 2013-10-18 2015-08-19 清华大学 A kind of Lithium-cathode semi-fuel cell component
CN107004879A (en) * 2014-11-25 2017-08-01 庄信万丰燃料电池有限公司 Film seal assembly
CN107004879B (en) * 2014-11-25 2020-06-05 庄信万丰燃料电池有限公司 Membrane seal assembly
CN105762396A (en) * 2016-03-03 2016-07-13 重庆大学 Flat-plate heat regeneration ammonium battery adopting foam metal electrode
CN105762396B (en) * 2016-03-03 2018-03-23 重庆大学 A kind of flat hot recycling ammonia battery using foam metal electrode
CN106374129A (en) * 2016-11-09 2017-02-01 大连融科储能技术发展有限公司 A flow battery stack sealing structure
CN106374129B (en) * 2016-11-09 2023-11-28 大连融科储能技术发展有限公司 A flow battery stack sealing structure
CN110571437A (en) * 2018-05-16 2019-12-13 嘉兴市兆业新能源技术有限公司 An anode structure for a fuel cell

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