Power generation device based on bipolar membrane and power generation method thereof

文档序号：1849346 发布日期：2021-11-16 浏览：17次中文

阅读说明：本技术 基于双极膜的发电装置及其发电方法 (Power generation device based on bipolar membrane and power generation method thereof ) 是由张旭刘武兴罗发宝毛悦李亚南于 2021-07-05 设计创作，主要内容包括：本发明提供一种基于双极膜的发电装置及其发电方法,涉及发电技术领域。本发明中双极膜膜堆的重复单元自阳电极至阴电极方向上依次叠压有第一阳离子交换膜、第一隔网、双极膜、第二隔网、阴离子交换膜、第三隔网和第二阳离子交换膜,并对应形成阳极室、碱室、酸室、盐室和阴极室五个隔室；通过在反向电渗析技术基础上引入上述双极膜构成反向双极膜电渗析,在隔室内分别通过酸和碱,酸碱中的氢离子和氢氧根离子分别透过双极膜的阳离子交换层和阴离子交换层在双极膜中间层上发生中和反应产生水,在双极膜上就产生pH梯度和由于酸性和碱性溶液的不同组成而产生的盐度梯度,从而实现将酸、碱溶液化学能向电能的有效转化；且能量密度高、理论膜堆电压高。(The invention provides a bipolar membrane-based power generation device and a power generation method thereof, and relates to the technical field of power generation. In the invention, a first cation exchange membrane, a first separation net, a bipolar membrane, a second separation net, an anion exchange membrane, a third separation net and a second cation exchange membrane are sequentially laminated in a repeating unit of the bipolar membrane stack from an anode to an cathode, and five compartments of an anode compartment, an alkali compartment, an acid compartment, a salt compartment and a cathode compartment are correspondingly formed; the bipolar membrane is introduced on the basis of a reverse electrodialysis technology to form reverse bipolar membrane electrodialysis, acid and alkali are respectively passed through in a compartment, hydrogen ions and hydroxide ions in the acid and the alkali respectively permeate a cation exchange layer and an anion exchange layer of the bipolar membrane to generate neutralization reaction on a bipolar membrane intermediate layer to generate water, a pH gradient and a salinity gradient generated due to different compositions of acidic and alkaline solutions are generated on the bipolar membrane, and therefore effective conversion of chemical energy of the acid and the alkaline solution to electric energy is achieved; and the energy density is high and the theoretical membrane stack voltage is high.)

1. A bipolar membrane based power generation device, comprising: the device comprises a bipolar membrane stack (1), an acid solution sample introduction device, an alkali solution sample introduction device, a saline solution sample introduction device, an electrode solution sample introduction device, an acid solution receiving device, an alkali solution receiving device, a saline solution receiving device, an electronic load (9), a cathode electrode (10) and an anode electrode (11);

the cathode electrode (10) and the anode electrode (11) are respectively arranged on two sides of the bipolar membrane stack (1); the bipolar membrane stack (1) at least comprises one repeating unit, wherein a first cation exchange membrane (22), a first separation net (23), a bipolar membrane (24), a second separation net (25), an anion exchange membrane (26), a third separation net (27) and a second cation exchange membrane (28) are sequentially laminated in the direction from the anode electrode (11) to the cathode electrode (10) of the repeating unit, five compartments of an anode compartment, an alkali compartment, an acid compartment, a salt compartment and a cathode compartment are correspondingly formed, and the first separation net (23), the second separation net (25) and the third separation net (27) are respectively positioned in the alkali compartment, the acid compartment and the salt compartment;

a first outlet pipe (14) of the acid solution sampling device is connected with a feeding port (2a) of the acid chamber, and a discharging port (2b) of the acid chamber is connected with a first inlet pipe (18) of the acid solution receiving device;

a second outlet pipe (15) of the alkali solution sample feeding device is connected with a feeding hole (3a) of the alkali chamber, and a discharging hole (3b) of the alkali chamber is connected with a second inlet pipe (19) of the alkali solution receiving device;

a third outlet pipe (16) of the saline solution sampling device is connected with a feeding hole (4a) of the saline chamber, and a discharging hole (4b) of the saline chamber is connected with a third inlet pipe (20) of the saline solution receiving device;

a fourth outlet pipe (17) of the electrode solution sample introduction device is connected with a cathode chamber feeding port (5a), a cathode chamber discharging port (5b) is connected with an anode chamber feeding port (5e), and an anode chamber discharging port (5f) is connected with a fourth inlet pipe (21) of the electrode solution sample introduction device;

the cathode electrode (10) is connected with a cathode (9b) of the electronic load (9), and the anode electrode (11) is connected with an anode (9a) of the electronic load (9).

2. The bipolar membrane-based power generation device according to claim 1,

the power generation device also comprises a first clamping device (12), a second clamping device (13) and gaskets, wherein the gaskets are respectively positioned between the negative electrode (10) and the positive electrode (11) and two sides of the bipolar membrane stack (1);

the cathode (10) is fixedly connected with one side of the bipolar membrane stack (1) through a first clamping device (12) and a gasket; the anode (11) is fixedly connected with the other side of the bipolar membrane stack (1) through a second clamping device (13) and a gasket;

the acid chamber feeding port (2a), the alkali chamber feeding port (3a), the salt chamber feeding port (4a), the cathode chamber feeding port (5a) and the cathode chamber discharging port (5b) are respectively positioned on one surface, far away from the cathode electrode (10), of the first clamping device (12);

and the acid chamber discharge hole (2b), the alkali chamber discharge hole (3b), the salt chamber discharge hole (4b), the anode chamber feed hole (5e) and the anode chamber discharge hole (5f) are respectively positioned on one surface, far away from the anode electrode (11), of the second clamping device (13).

3. The bipolar membrane-based power generation device according to any one of claims 1-2,

the acid solution sampling device further comprises an acid solution containing container (2c) and an acid solution conveying device (2d), the first outlet pipe (14) is connected with the acid chamber feed port (2a) through a first connecting device, and the acid solution conveying device (2d) is arranged on the first outlet pipe (14);

the discharge port (2b) of the acid chamber is connected with the first inlet pipe (18) through a second connecting device.

4. The bipolar membrane-based power generation device according to any one of claims 1-2,

the alkali solution sample introduction device further comprises an alkali solution containing container (3c) and an acid solution conveying device (3d), the second outlet pipe (15) is connected with the alkali chamber feeding hole (3a) through a third connecting device, and the alkali solution conveying device (3d) is arranged on the second outlet pipe (15);

the discharge hole (3b) of the alkali chamber is connected with the second inlet pipe (19) through a fourth connecting device.

5. The bipolar membrane-based power generation device according to any one of claims 1-2,

the saline solution sampling device further comprises a saline solution containing container (4c) and a saline solution conveying device (4d), the third outlet pipe (16) is connected with the salt chamber feeding hole (4a) through a fifth connecting device, and the saline solution conveying device (4d) is arranged on the third outlet pipe (16);

the discharge hole (4b) of the salt chamber is connected with the third inlet pipe (20) through a sixth connecting device.

6. The bipolar membrane-based power generation device according to any one of claims 1-2,

the electrode solution sampling device further comprises an electrode solution containing container (5c) and a saline solution conveying device (5d), the fourth outlet pipe (17) is connected with the cathode chamber feeding port (5a) through a seventh connecting device, and the saline solution conveying device (5d) is arranged on the seventh connecting device;

the discharge hole (5b) of the cathode chamber is connected with the feed hole (5e) of the anode chamber through an eighth connecting device;

the discharge port (5f) of the anode chamber is connected with the fourth inlet pipe (21) through a ninth connecting device.

7. A power generation method of the bipolar membrane-based power generation device according to claim 1, comprising:

delivering an acid solution to an acid chamber of the bipolar membrane stack (1) through an acid solution sample injection device;

conveying the alkali solution into an alkali chamber of the bipolar membrane stack (1) through an alkali solution sample introduction device;

conveying a salt solution into a salt chamber of the bipolar membrane stack (1) through a salt solution sample introduction device;

sequentially conveying electrode liquid to a cathode chamber and an anode chamber of the bipolar membrane stack (1) through an electrode liquid sample introduction device, and collecting the electrode liquid sample introduction device;

collecting the acid solution passing through the acid chamber of the bipolar membrane stack (1) into an acid solution receiving device;

collecting the alkaline solution passing through the alkaline chamber of the bipolar membrane stack (1) into an alkaline solution receiving device;

collecting the salt solution passing through the salt chamber of the bipolar membrane stack (1) into a salt solution receiving device.

8. The method of power generation as claimed in claim 7,

the acid solution is one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, acetic acid and formic acid solution;

and/or the alkali solution is selected from one or more of sodium hydroxide, potassium hydroxide and ammonia water solution;

and/or the salt solution is selected from one or more of sodium chloride, sodium nitrate, sodium sulfate, sodium phosphate, sodium acetate, sodium formate, potassium chloride, potassium nitrate, potassium sulfate, potassium phosphate, potassium acetate, potassium formate, ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium acetate and ammonium formate;

and/or the electrode solution is selected from one or more of sodium sulfate, sodium chloride, ferric chloride, potassium ferricyanide and potassium ferrocyanide solution.

9. The power generation method according to any one of claims 7 to 8,

the concentration of the acid solution is 0.1-5.0 mol/L;

and/or the concentration of the alkali solution is 0.1-5.0 mol/L;

and/or the concentration of the salt solution is 0.01-3.0 mol/L;

and/or the concentration of the electrode liquid is 0.05-2.0 mol/L.

10. The method for power generation according to any one of claims 7 to 8, wherein the electrolyte is 0.05 to 2.0mol/L K₃[Fe(CN)₆]、0.05～2.0mol/L K₄[Fe(CN)₆]And 0.05-2.0 mol/L NaCl.

Technical Field

The invention relates to the technical field of power generation, in particular to a power generation device based on a bipolar membrane and a power generation method thereof.

Background

The energy is the basis of national economy development, and the high-quality development of economy cannot be separated from the high-quality development of energy. Fossil energy provides sufficient power and material basis for the development of economic society in China, but faces the pressure of exhaustion crisis, environmental pollution and the like, and the electricity generation by the traditional fossil energy is not long-term. Therefore, development of new energy is urgently required. Nowadays, emerging technologies such as solar power generation and wind power generation are gradually emerging, and particularly after 2019, wind power becomes the third largest power source in China after coal power and water power. The emerging power generation technologies effectively relieve the problems of fossil energy crisis, environmental pollution and the like. However, these emerging power generation technologies suffer from uncontrollable factors such as instability, high cost, geographical limitations, etc.

In recent years, a reverse electrodialysis power generation technology using a concentration gradient difference as a driving force has been developed and utilized gradually due to its low cost and stable technology. The reverse electrodialysis power generation technology is a process for converting the salt difference energy between high-concentration salt solution and low-concentration salt solution into electric energy. Because concentration difference exists between the concentrated water and the fresh water, ions can migrate from the concentrated water to the fresh water, anion exchange membranes and cation exchange membranes in the reverse electrodialysis device are alternately arranged under the interval action of the partition plates, so that the migration of the ions forms directional movement, an internal current is formed in the battery, the internal current can be converted into an external current through oxidation-reduction reaction at the electrode of the reverse electrodialysis device, the current is led out through a lead, and therefore the salt difference energy is converted into electric energy.

For example, a reverse electrodialysis pilot project at Dutch scale of 1 kW/10 kWh has been in operation for supplying electricity to nearby student dormitories since 2018 (Membranes,2020,10(12): 409.). For another example, chinese patent CN201711421091.6 discloses a system and a method for driving bipolar membrane electrodialysis to generate acid and alkali by reverse electrodialysis, and specifically, the technology is to introduce two salt solutions with different concentrations into a membrane stack of reverse electrodialysis to realize the conversion of salt difference energy into electric energy without applying an external power supply, and the electric energy generated by the membrane stack of reverse electrodialysis drives bipolar membranes to perform water dissociation to obtain hydrogen ions and hydroxyl ions; the method provides a specific application of the reverse electrodialysis, does not need energy storage and conversion in the whole process, and has a simple process.

However, the reverse electrodialysis technique relies on the difference between the concentrations of the solutions on both sides of the ion exchange membrane to drive the ion migration, i.e., the membrane potential is mainly determined by the ratio of the activities of the high-concentration salt solution and the low-concentration salt solution on both sides of the ion exchange membrane. The activity ratio of the solution on two sides of the ion exchange membrane can only reach hundreds of times at most due to the limitation of the saturated concentration of the solution, so that the theoretical membrane potential provided by the existing reverse electrodialysis technology is limited and the energy density is not high.

Disclosure of Invention

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides a bipolar membrane-based power generation device and a power generation method thereof, and solves the technical problems of limited theoretical membrane potential and low energy density provided by the existing reverse electrodialysis technology.

(II) technical scheme

In order to achieve the purpose, the invention is realized by the following technical scheme:

a bipolar membrane based power generation device comprising: the system comprises a bipolar membrane stack, an acid solution sample introduction device, an alkali solution sample introduction device, a saline solution sample introduction device, an electrode solution sample introduction device, an acid solution receiving device, an alkali solution receiving device, a saline solution receiving device, an electronic load, a cathode electrode and an anode electrode;

the cathode electrode and the anode electrode are respectively arranged on two sides of the bipolar membrane stack; the bipolar membrane stack at least comprises one repeating unit, wherein a first cation exchange membrane, a first separation net, a bipolar membrane, a second separation net, an anion exchange membrane, a third separation net and a second cation exchange membrane are sequentially laminated in the direction from the anode to the cathode, and correspondingly form five compartments of an anode compartment, an alkali compartment, an acid compartment, a salt compartment and a cathode compartment, and the first separation net, the second separation net and the third separation net are respectively positioned in the alkali compartment, the acid compartment and the salt compartment;

a first outlet pipe of the acid solution sample introduction device is connected with a feed inlet of the acid chamber, and a discharge outlet of the acid chamber is connected with a first inlet pipe of the acid solution receiving device;

a second outlet pipe of the alkali solution sample introduction device is connected with a feed inlet of the alkali chamber, and a discharge outlet of the alkali chamber is connected with a second inlet pipe of the alkali solution receiving device;

a third outlet pipe of the saline solution sampling device is connected with a feed inlet of the saline chamber, and a discharge outlet of the saline chamber is connected with a third inlet pipe of the saline solution receiving device;

a fourth outlet pipe of the electrode solution sampling device is connected with a cathode chamber feeding port, a cathode chamber discharging port is connected with an anode chamber feeding port, and an anode chamber discharging port is connected with a fourth inlet pipe of the electrode solution sampling device;

the cathode electrode is connected with the negative electrode of the electronic load, and the anode electrode is connected with the positive electrode of the electronic load.

Preferably, the power generation device further comprises a first clamping device, a second clamping device and a gasket, wherein the gasket is respectively positioned between the cathode electrode and the anode electrode and two sides of the bipolar membrane stack.

The cathode electrode is fixedly connected with one side of the bipolar membrane stack through a first clamping device and a gasket; the anode is fixedly connected with the other side of the bipolar membrane stack through a second clamping device and a gasket;

the acid chamber feed inlet, the alkali chamber feed inlet, the salt chamber feed inlet, the cathode chamber feed inlet and the cathode chamber discharge outlet are respectively positioned on one surface of the first clamping device, which is far away from the cathode electrode;

the discharge port of the acid chamber, the discharge port of the alkali chamber, the discharge port of the salt chamber, the feed port of the anode chamber and the discharge port of the anode chamber are respectively positioned on one surface of the second clamping device, which is far away from the anode electrode.

Preferably, the acid solution sampling device further comprises an acid solution containing container and an acid solution conveying device, the first outlet pipe is connected with the feeding port of the acid chamber through a first connecting device, and the acid solution conveying device is arranged on the first outlet pipe;

and the discharge port of the acid chamber is connected with the first inlet pipe through a second connecting device.

Preferably, the alkali solution sample introduction device further comprises an alkali solution containing container and an acid solution conveying device, the second outlet pipe is connected with the feed inlet of the alkali chamber through a third connecting device, and the alkali solution conveying device is arranged on the second outlet pipe;

and the discharge hole of the alkali chamber is connected with the second inlet pipe through a fourth connecting device.

Preferably, the saline solution sampling device further comprises a saline solution containing container and a saline solution conveying device, the third outlet pipe is connected with the feed inlet of the saline chamber through a fifth connecting device, and the saline solution conveying device is arranged on the third outlet pipe;

and the discharge hole of the salt chamber is connected with the third inlet pipe through a sixth connecting device.

Preferably, the electrode solution sampling device further comprises an electrode solution containing container and a saline solution conveying device, the fourth outlet pipe is connected with the feed inlet of the cathode chamber through a seventh connecting device, and the saline solution conveying device is arranged on the seventh connecting device;

the discharge hole of the cathode chamber is connected with the feed hole of the anode chamber through an eighth connecting device;

and the discharge port of the anode chamber is connected with the fourth inlet pipe through a ninth connecting device.

A power generation method of the bipolar membrane-based power generation device as described above, comprising:

conveying the acid solution to an acid chamber of the bipolar membrane stack through an acid solution sample introduction device;

conveying the alkali solution into an alkali chamber of the bipolar membrane stack through an alkali solution sample introduction device;

conveying the salt solution to a salt chamber of the bipolar membrane stack through a salt solution sample introduction device;

sequentially conveying electrode liquid to a cathode chamber and an anode chamber of the bipolar membrane stack through an electrode liquid sample introduction device, and collecting the electrode liquid sample introduction device;

collecting the acid solution passing through the acid chamber of the bipolar membrane stack into an acid solution receiving device;

collecting the alkaline solution passing through the alkaline chamber of the bipolar membrane stack into an alkaline solution receiving device;

collecting the salt solution passing through the salt chamber of the bipolar membrane stack into a salt solution receiving device.

Preferably, the acid solution is one or more selected from sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, acetic acid and formic acid solution;

preferably, the alkali solution is selected from one or more of sodium hydroxide, potassium hydroxide and ammonia water solution;

preferably, the salt solution is selected from one or more of sodium chloride, sodium nitrate, sodium sulfate, sodium phosphate, sodium acetate, sodium formate, potassium chloride, potassium nitrate, potassium sulfate, potassium phosphate, potassium acetate, potassium formate, ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium acetate and ammonium formate;

preferably, the electrode solution is one or more selected from sodium sulfate, sodium chloride, ferric chloride, potassium ferricyanide and potassium ferrocyanide solution.

Preferably, the concentration of the acid solution is 0.1-5.0 mol/L;

preferably, the concentration of the alkali solution is 0.1-5.0 mol/L;

preferably, the concentration of the salt solution is 0.01-3.0 mol/L;

preferably, the concentration of the electrode liquid is 0.05-2.0 mol/L.

Preferably, the electrode solution is 0.05-2.0 mol/L K₃[Fe(CN)₆]、0.05～2.0mol/LK₄[Fe(CN)₆]And 0.05-2.0 mol/L NaCl.

(III) advantageous effects

The invention provides a bipolar membrane-based power generation device and a power generation method thereof. Compared with the prior art, the method has the following beneficial effects:

according to the invention, a cathode electrode and an anode electrode are respectively arranged on two sides of a bipolar membrane stack, the bipolar membrane stack at least comprises a repeating unit, a first cation exchange membrane, a first separation net, a bipolar membrane, a second separation net, an anion exchange membrane, a third separation net and a second cation exchange membrane are sequentially laminated in the direction from the anode electrode to the cathode electrode in the repeating unit, and five compartments of an anode compartment, an alkali compartment, an acid compartment, a salt compartment and a cathode compartment are correspondingly formed; the bipolar membrane stack is introduced on the basis of a reverse electrodialysis technology to form reverse bipolar membrane electrodialysis, acid and alkali pass through an acid chamber and an alkali chamber on two sides of a bipolar membrane respectively, and hydrogen ions and hydroxide ions in the acid and the alkali permeate through a cation exchange layer and an anion exchange layer of the bipolar membrane respectively to generate water through neutralization reaction on a bipolar membrane middle layer, so that two gradients are generated on the bipolar membrane: the pH gradient and the salinity gradient generated by different compositions of the acidic solution and the alkaline solution, thereby realizing the effective conversion of the chemical energy of the acidic solution and the alkaline solution into the electric energy; the whole process can be carried out at normal temperature, the raw materials are wide in source and low in price, the energy density is high, the theoretical membrane stack voltage is high, the generated energy can be flexibly adjusted, and the safety performance is high.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a schematic structural diagram of a bipolar membrane-based power generation device provided by an embodiment of the invention;

FIG. 2 is a schematic diagram of the internal structure principle of a bipolar membrane stack of a bipolar membrane-based power generation device provided by an embodiment of the invention, wherein only one repeating unit is included;

FIG. 3 is a schematic diagram of the internal structure of a bipolar membrane stack of a bipolar membrane-based power generation device provided by an embodiment of the invention, wherein only one repeating unit is included;

fig. 4 is a schematic structural diagram of a separation net according to an embodiment of the present invention;

FIG. 5 is a graph showing the variation of the open-circuit voltage of the membrane stack with the flow rate in examples 1 to 5 of the present invention;

FIG. 6 is a graph showing the variation of the open-circuit voltage of the membrane stack with the flow rate in examples 6 to 8 of the present invention;

FIG. 7 is a graph showing the variation of the open-circuit voltage of the film stack with concentration according to examples 9-11 of the present invention.

Wherein, the bipolar membrane stack 1, the first cation exchange membrane 22, the first separation net 23, the bipolar membrane 24, the second separation net 25, the anion exchange membrane 26, the third separation net 27, the second cation exchange membrane 28, the electronic load 9, the anode 9a, the cathode 9b, the cathode 10, the anode 11, the first clamping device 12, the second clamping device 13, the first outlet pipe 14, the second outlet pipe 15, the third outlet pipe 16, the fourth outlet pipe 17, the first inlet pipe 18, the second inlet pipe 19, the third inlet pipe 20, the fourth inlet pipe 21, the acid chamber inlet 2a, the acid chamber outlet 2b, the acid solution containing container 2c, the acid solution conveying device 2d, the alkali chamber inlet 3a, the alkali chamber outlet 3b, the alkali solution containing container 3c, the acid solution conveying device 3d, the salt chamber inlet 4a, the salt chamber outlet 4b, the salt solution containing container 4c, the salt solution outlet 25, the anion exchange membrane 26, the third separation net 27, the second cation exchange membrane 28, the electronic load 9, the anode 9a, the cathode 9b, the cathode 10, the cathode 11, the anode 11, the acid chamber outlet pipe 20, the acid chamber inlet 21, the acid chamber inlet 2a, the acid chamber inlet 2b, the acid chamber outlet 2b, the salt solution containing container 2c, the salt solution containing container 4c, the salt solution containing container, and the salt solution container 4b, The device comprises a saline solution conveying device 4d, a cathode chamber feeding port 5a, a cathode chamber discharging port 5b, an electrode solution containing container 5c, a saline solution conveying device 5d, an anode chamber feeding port 5e, an anode chamber discharging port 5f, an acid solution receiving container 6c, an alkali solution receiving container 7c and a saline solution receiving container 8 c.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The embodiment of the application provides a power generation device based on a bipolar membrane and a power generation method thereof, solves the technical problems of limited theoretical membrane potential and low energy density provided by the existing reverse electrodialysis technology, and achieves the beneficial effects of retaining the advantages of stable reverse electrodialysis power generation technology and low cost and overcoming the defects of limited theoretical membrane potential, low energy density and the like.

In order to solve the technical problems, the general idea of the embodiment of the application is as follows:

in the embodiment of the invention, a cathode electrode and an anode electrode are respectively arranged on two sides of a bipolar membrane stack, the bipolar membrane stack at least comprises a repeating unit, and a first cation exchange membrane, a first separation net, a bipolar membrane, a second separation net, an anion exchange membrane, a third separation net and a second cation exchange membrane are sequentially laminated in the direction from the anode electrode to the cathode electrode in the repeating unit, and five compartments of an anode compartment, an alkali compartment, an acid compartment, a salt compartment and a cathode compartment are correspondingly formed; the bipolar membrane stack is introduced on the basis of a reverse electrodialysis technology to form reverse bipolar membrane electrodialysis, acid and alkali pass through an acid chamber and an alkali chamber on two sides of a bipolar membrane respectively, and hydrogen ions and hydroxide ions in the acid and the alkali permeate through a cation exchange layer and an anion exchange layer of the bipolar membrane respectively to generate water through neutralization reaction on a bipolar membrane middle layer, so that two gradients are generated on the bipolar membrane: the pH gradient and the salinity gradient generated by different compositions of the acidic solution and the alkaline solution, thereby realizing the effective conversion of the chemical energy of the acidic solution and the alkaline solution into the electric energy; the whole process can be carried out at normal temperature, the raw materials are wide in source and low in price, the energy density is high, the theoretical membrane stack voltage is high, the generated energy can be flexibly adjusted, and the safety performance is high.

In order to better understand the technical solution, the technical solution will be described in detail with reference to the drawings and the specific embodiments.

In a first aspect, as shown in fig. 1 to 4, an embodiment of the present invention provides a bipolar membrane-based power generation device, including: the device comprises a bipolar membrane stack 1, an acid solution sample introduction device, an alkali solution sample introduction device, a saline solution sample introduction device, an electrode solution sample introduction device, an acid solution receiving device, an alkali solution receiving device, a saline solution receiving device, an electronic load 9, a cathode electrode 10, an anode electrode 11, a first clamping device 12, a second clamping device 13 and a gasket.

The cathode electrode 10 and the anode electrode 11 are respectively arranged on two sides of the bipolar membrane stack 1.

As shown in fig. 2 to 3, the bipolar membrane stack 1 includes at least one repeating unit, and the repeating unit is formed by sequentially laminating a first cation exchange membrane 22, a first separation net 23, a bipolar membrane 24, a second separation net 25, an anion exchange membrane 26, a third separation net 27 and a second cation exchange membrane 28 from the anode 11 to the cathode 10, and correspondingly forming five compartments, namely an anode compartment, an alkali compartment, an acid compartment, a salt compartment and a cathode compartment.

Specifically, an anode chamber is formed between the anode electrode 11 and the first cation exchange membrane 22, an alkali chamber is formed between the first cation exchange membrane 22 and the bipolar membrane 24, an acid chamber is formed between the bipolar membrane 24 and the anion exchange membrane 26, a salt chamber is formed between the anion exchange membrane 26 and the second cation exchange membrane 28, and a cathode chamber is formed between the second cation exchange membrane 28 and the cathode electrode 10; the first separation net 23, the second separation net 25 and the third separation net 27 are respectively positioned in the alkali chamber, the acid chamber and the salt chamber.

In the embodiment of the invention, the bipolar membrane stack 1 can comprise 1-30 repeating units; in another embodiment, the bipolar membrane stack 1 can also comprise 3-20 repeating units; in other embodiments, the bipolar membrane stack 1 may further include 5 repeating units.

In the embodiment of the present invention, the effective area of each of the first cation exchange membrane 22, the bipolar membrane 24, the anion exchange membrane 26, the third separation net 27 and the second cation exchange membrane 28 may be 140-220 cm²(ii) a In another embodiment, the effective area of each of the first cation exchange membrane 22, the bipolar membrane 24, the anion exchange membrane 26, the third separation net 27 and the second cation exchange membrane 28 can also be 160-200 cm²(ii) a In other embodiments, the effective area of each of the first cation exchange membrane 22, bipolar membrane 24, anion exchange membrane 26, third mesh 27 and second cation exchange membrane 28 may also be 188.2cm²。

Each separation net is positioned between the ion exchange membrane and the ion exchange membrane, the material is preferably polystyrene, and the edge preferably comprises small holes; as shown in fig. 4, the small holes include a sealed small hole and an open small hole, the sealed small hole is used for enabling the liquid to flow through the whole membrane stack, and the opening direction of the open small hole is preferably the middle part of the separation net, so that the solution is subjected to mass transfer exchange in the flow passage separation net on one hand and flows out in the direction of the open small hole on the other hand.

The first cation exchange membrane 22, the bipolar membrane 24, the anion exchange membrane 26, the third separation net 27 and the second cation exchange membrane 28 preferably also comprise small holes which are closed small holes and are positioned at the edges of the membranes. The ion exchange between each of the separate compartments is enabled by the composition of the membrane and the spacer mesh and the arrangement of the small holes.

As shown in fig. 1, the first outlet pipe 14 of the acid solution sample feeding device is connected with the acid chamber feed port 2a, and the acid chamber discharge port 2b is connected with the first inlet pipe 18 of the acid solution receiving device.

The acid solution sampling device further comprises an acid solution containing container 2c and an acid solution conveying device 2 d. In order to facilitate the circulation flow of the acid solution, the first outlet pipe 14 is connected with the acid chamber feed port 2a through a first connecting device, and the acid solution delivery device 2d is arranged on the first outlet pipe 14; the discharge port 2b of the acid chamber is connected with the first inlet pipe 18 through a second connecting device.

In the embodiment of the present invention, the acid solution container 2c is used for containing an acid solution, and there is no special limitation on the shape, material and size of the acid solution container, and the acid solution container may be an acid chamber feeding tank, if the actual operation conditions are met; the acid solution conveying device 2d is used for conveying the acid solution in the acid solution containing container 2c to the acid chamber, and may be an acid chamber feeding peristaltic pump; the acid solution receiving device preferably comprises an acid solution receiving container 6c, and the acid solution receiving container 6c can be an acid chamber discharge tank; the first connecting device and the second connecting device can be latex tubes.

As shown in fig. 1, the second outlet pipe 15 of the alkali solution feeding device is connected with the inlet port 3a of the alkali chamber, and the outlet port 3b of the alkali chamber is connected with the second inlet pipe 19 of the alkali solution receiving device.

The alkali solution sample introduction device further comprises an alkali solution containing container 3c and an acid solution conveying device 3 d. In order to facilitate the circulation flow of the alkali solution, the second outlet pipe 15 is connected with the alkali chamber feed port 3a through a third connecting device, and the alkali solution delivery device 3d is arranged on the second outlet pipe 15; the discharge port 3b of the alkali chamber is connected with the second inlet pipe 19 through a fourth connecting device.

In the embodiment of the present invention, the alkaline solution holding container 3c is used for holding an alkaline solution, and there is no special limitation on the shape, material and size of the alkaline solution holding and receiving container, and the container may be an alkaline chamber feeding tank, if the actual operation conditions are met; the alkali solution conveying device 3d is used for conveying the alkali solution in the alkali solution holding container 3c to the alkali chamber, and can be an alkali chamber feeding peristaltic pump; the caustic solution receiving means preferably comprises a caustic solution receiving vessel 7c, which caustic solution receiving vessel 7c may be a caustic chamber discharge tank; the third connecting device and the fourth connecting device can be latex tubes.

As shown in fig. 1, the third outlet pipe 16 of the saline solution sampling device is connected to the salt chamber inlet 4a, and the salt chamber outlet 4b is connected to the third inlet pipe 20 of the saline solution receiving device.

The saline solution sampling device further comprises a saline solution containing container 4c and a saline solution conveying device 4 d. In order to facilitate the circulation of the saline solution, the third outlet pipe 16 is connected with the salt chamber feed port 4a through a fifth connecting device, and the saline solution delivery device 4d is arranged on the third outlet pipe 16; the salt chamber discharge port 4b is connected with the third inlet pipe 20 through a sixth connecting device.

In the embodiment of the present invention, the saline solution container 4c is used for containing saline solution, and may be a saline chamber feeding tank; the saline solution conveying device 4d is used for conveying the saline solution in the saline solution containing container 4c to the salt chamber, and can be a salt chamber feeding peristaltic pump; the saline solution receiving device preferably comprises a saline solution receiving container 8c, and the saline solution receiving container 8c can be a salt chamber discharge tank; the fifth connecting device and the sixth connecting device can be latex tubes.

As shown in fig. 1, the fourth outlet pipe 17 of the electrode solution sampling device is connected to the cathode chamber inlet 5a, the cathode chamber outlet 5b is connected to the anode chamber inlet 5e, and the anode chamber outlet 5f is connected to the fourth inlet pipe 21 of the electrode solution sampling device.

The electrode solution sampling device further comprises an electrode solution containing container 5c and a saline solution conveying device 5 d. In order to facilitate the circulation flow of the electrode solution, the fourth outlet pipe 17 is connected with the cathode chamber feed port 5a through a seventh connecting device, and the saline solution conveying device 5d is arranged on the seventh connecting device; the discharge port 5b of the cathode chamber is connected with the feed port 5e of the anode chamber through an eighth connecting device; the anode chamber discharge port 5f is connected with the fourth inlet pipe 21 through a ninth connecting device, so that a circulation loop is formed between the electrode liquid feeding device 5 and the cathode and anode chambers. In particular, the fourth outlet duct 17 may be identical to the fourth inlet duct 21 or may be different.

In the embodiment of the present invention, the electrode solution container 5c is used for containing electrode solution, and may be an electrode chamber tank; the electrode liquid conveying device 5d is used for conveying the electrode liquid in the electrode liquid holding container 5c to the electrode chamber, and can be an electrode chamber peristaltic pump; the seventh connecting device, the eighth connecting device and the ninth connecting device can be latex tubes.

As shown in fig. 1, the cathode electrode 10 is connected to the negative electrode 9b of the electronic load 9, and the anode electrode 11 is connected to the positive electrode 9a of the electronic load 9.

The gaskets are respectively positioned between the negative electrode 10 and the positive electrode 11 and two sides of the bipolar membrane stack 1; the cathode 10 is fixedly connected with one side of the bipolar membrane stack 1 through a first clamping device 12 and a gasket; the anode 11 is fixedly connected with the other side of the bipolar membrane stack 1 through a second clamping device 13 and a gasket.

The cathode electrode 10 and the anode electrode 11 are selected from at least one of a nickel sheet, a titanium sheet, a stainless steel sheet, a foamed nickel sheet, a foamed titanium sheet, a nickel mesh, a titanium mesh, and a stainless steel mesh coated with a catalyst on the surface, and the catalyst is selected from at least one of platinum, ruthenium, iridium, and oxides or sulfides thereof.

The embodiment of the present invention does not have any special limitation on the first clamping device 12 and the second clamping device 13, and may satisfy actual operating conditions. For example, the first clamping device 12 and the second clamping device 13 may be composed of clamping plates and bolts, that is, two clamping plates are respectively disposed on both sides of the bipolar membrane stack 1 and fastened by bolts.

As shown in fig. 1, the acid chamber inlet 2a, the alkali chamber inlet 3a, the salt chamber inlet 4a, the cathode chamber inlet 5a and the cathode chamber outlet 5b are respectively located at different positions on a side of the first clamping device 12 away from the cathode 10; the acid chamber discharge port 2b, the alkali chamber discharge port 3b, the salt chamber discharge port 4b, the anode chamber feed port 5e and the anode chamber discharge port 5f are respectively positioned at different positions on one surface of the second clamping device 13, which is far away from the anode 11.

The working principle of the power generation device provided by the embodiment of the invention is as follows:

the bipolar membrane stack is introduced on the basis of a reverse electrodialysis technology to form reverse bipolar membrane electrodialysis, acid and alkali pass through an acid chamber and an alkali chamber on two sides of a bipolar membrane respectively, and hydrogen ions and hydroxide ions in the acid and the alkali permeate through a cation exchange layer and an anion exchange layer of the bipolar membrane respectively to generate water through neutralization reaction on a bipolar membrane middle layer, so that two gradients are generated on the bipolar membrane: pH gradient and salinity gradient due to different compositions of acidic and alkaline solutions, thereby achieving effective conversion of chemical energy of acidic and alkaline solutions to electric energy.

Because the existing reverse electrodialysis technology depends on the concentration difference of solutions at two sides of an ion exchange membrane to drive ion migration, the theoretical membrane potential can be calculated by the Nernst equation as follows:

wherein α is the permselectivity of the ion-exchange membrane, R is the gas constant, T is the absolute temperature, F is the Faraday constant, a_{Height of}Ion activity of high concentration salt solution, a_{Is low in}The ionic activity of the low-concentration salt solution is shown, and z is the ionic valence.

It can be seen that the membrane potential is mainly determined by the activity ratio of the high and low concentration salt solutions on both sides of the ion exchange membrane. However, limited by the saturation concentration of the solution, for example, the concentration of the saturated sodium chloride solution is 6mol/L, and the activity ratio of the solution on both sides of the ion exchange membrane is up to several hundred times, so that the reverse electrodialysis provides a limited theoretical membrane potential and a low energy density.

The embodiment of the invention is different from the salt solution in that the saturated concentration of the acid and alkali solution is higher, for example, the concentration of concentrated hydrochloric acid and saturated sodium hydroxide can be up to 13.75mol/L and 20mol/L, so the theoretical energy storage density is higher. Likewise, the theoretical membrane potential of a bipolar membrane can be calculated according to the nernst equation:

wherein alpha is_CEL、α_AELIs the selective permeability of an anode membrane layer and a cathode membrane layer of the bipolar membrane, R is a gas constant, T is an absolute temperature, F is a Faraday constant, a is an ionic activity,is the ionic valence state of hydrogen ion and hydroxyl ion,the activity of hydrogen ions on the anode layer of the bipolar membrane,is the activity of hydrogen ions on the intermediate layer of the bipolar membrane,the activity of hydroxyl ions on the cathode layer of the bipolar membrane,the activity of hydroxide ions on the middle layer of the bipolar membrane,as average ion activity, K_WIs the dissociation constant of water.

Therefore, the theoretical membrane provided by the embodiment of the invention has high voltage, and can effectively overcome the defect of low energy density of the reverse electrodialysis power generation technology; the whole process can be carried out at normal temperature, the raw materials are wide in source and low in price, the energy density is high, the theoretical membrane stack voltage is high, the generated energy can be flexibly adjusted, and the safety performance is high.

In a second aspect, the embodiment of the present invention also provides a power generation method of the above bipolar membrane-based power generation device, including:

conveying an acid solution to an acid chamber of the bipolar membrane stack 1 through an acid solution sample introduction device;

conveying the alkali solution into an alkali chamber of the bipolar membrane stack 1 through an alkali solution sample introduction device;

conveying the salt solution to a salt chamber of the bipolar membrane stack 1 through a salt solution sample introduction device;

sequentially conveying electrode liquid to a cathode chamber and an anode chamber of the bipolar membrane stack 1 through an electrode liquid sample introduction device, and collecting the electrode liquid sample introduction device;

collecting the acid solution passing through the acid chamber of the bipolar membrane stack 1 into an acid solution receiving device;

collecting the alkaline solution passing through the alkaline chamber of the bipolar membrane stack 1 into an alkaline solution receiving device;

the salt solution passing through the salt chamber of the bipolar membrane stack 1 is collected into a salt solution receiving device.

The hydrogen ions in the acid chamber acid solution and the hydroxide ions in the alkali chamber alkali solution diffuse to the middle layer of the bipolar membrane 24 to perform acid-base neutralization reaction, thereby causing the directional movement of ions. Under the directional movement of ions caused by acid-base neutralization reaction in the middle of the bipolar membrane 24, acid radical ions in the acid chamber acid solution and cations in the base chamber alkali solution migrate to the salt chamber, and then the conversion of chemical energy of the acid-base solution to electric energy can be realized by combining with redox reaction of the electrode solution.

In the embodiment of the present invention, the acid solution is preferably one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and formic acid solution, more preferably one or more of hydrochloric acid, sulfuric acid, and phosphoric acid solution, and most preferably a hydrochloric acid solution. In the embodiment of the invention, the concentration of the acid solution is preferably 0.1-5 mol/L, more preferably 0.1-4 mol/L, most preferably 0.3-0.7 mol/L, and most preferably 0.5 mol/L.

In the embodiment of the present invention, the alkali solution is preferably one or more of sodium hydroxide, potassium hydroxide and an aqueous ammonia solution, more preferably one or more of sodium hydroxide and a potassium hydroxide solution, and most preferably a sodium hydroxide solution. In the invention, the concentration of the alkali solution is preferably 0.1-5 mol/L, more preferably 0.1-4 mol/L, most preferably 0.3-0.7 mol/L, and most preferably 0.5 mol/L.

In the embodiment of the present invention, the salt solution is preferably one or more of a solution of sodium chloride, sodium nitrate, sodium sulfate, sodium phosphate, sodium acetate, sodium formate, potassium chloride, potassium nitrate, potassium sulfate, potassium phosphate, potassium acetate, potassium formate, ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium acetate, and ammonium formate, more preferably one or more of a solution of sodium chloride, potassium chloride, and ammonium chloride, and most preferably a solution of sodium chloride. In the invention, the concentration of the salt solution is preferably 0.01-3 mol/L, more preferably 0.01-2 mol/L, most preferably 0.01-0.1 mol/L, and most preferably 0.03 mol/L.

In the embodiment of the present invention, the electrode solution is preferably an inorganic salt solution, more preferably one or more of an inorganic salt solution sodium sulfate, sodium chloride, ferric chloride, potassium ferricyanide, and potassium ferrocyanide solution, and most preferably a mixed solution of sodium chloride, potassium ferricyanide, and potassium ferrocyanide. In the embodiment of the invention, the concentration of the electrode liquid is preferably 0.1-5.0 mol/L, specifically 0.05-2.0 mol/L K₃[Fe(CN)₆]、0.05～2.0mol/L K₄[Fe(CN)₆]And 0.05 to 2.0mol/L NaCl, more preferably 0.075 to 1.0mol/L K₃[Fe(CN)₆]、0.075～1.0mol/LK₄[Fe(CN)₆]And 0.075-1.0 mol/L NaCl, most preferably 0.1mol/LK3[ Fe (CN)6]、0.1mol/L K4[Fe(CN)6]And 0.25mol/L NaCl.

In the present embodiment, before the apparatus is operated, it is preferable to flow the solution inside the apparatus to discharge bubbles; after the air bubbles are discharged, the electronic load 9 is connected to operate the apparatus. More preferably, the solution flowing is realized by starting a peristaltic pump, so that the solutions in the anode chamber, the cathode chamber, the acid chamber, the alkali chamber and the salt chamber respectively flow.

It can be understood that the power generation method provided by the embodiment of the present invention corresponds to the power generation device based on the bipolar membrane provided by the embodiment of the present invention, and for the explanation, examples, beneficial effects and other parts of the relevant contents, reference may be made to the corresponding parts in the power generation device based on the bipolar membrane, and details are not described here.

For further understanding of the present invention, the bipolar membrane-based power generation apparatus and the method thereof provided by the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.

Example 1:

assembling the device: specifically, an anion exchange membrane, a cation exchange membrane and a bipolar membrane are sequentially laminated and then added with a bipolar membrane stack 1 consisting of 5 groups of repeating units formed by auxiliary materials such as a flow passage separation net, a sealing gasket and the like, wherein the anion exchange membrane and the cation exchange membrane are commercially available inlet membranes, the bipolar membrane is a commercially available domestic membrane, and the effective area of each membrane is 188.2cm²The bipolar membrane device is formed by clamping titanium ruthenium-coated cathode and anode electrodes 10 and 11 respectively arranged at two ends of a membrane stack and clamping devices 12 and 13 arranged at two ends of the electrodes through bolts, a cathode chamber feed inlet 5a and a discharge outlet 5b of the bipolar membrane device, an anode chamber feed inlet 5e and a discharge outlet 5f of the bipolar membrane device, an acid chamber feed inlet 2a and a discharge outlet 2b of the bipolar membrane device, an alkali chamber feed inlet 3a and a discharge outlet 3b of the bipolar membrane device, and a salt chamber feed inlet 4a and a discharge outlet 4b of the bipolar membrane device are respectively connected to corresponding electrode chamber tanks, acid chamber feed tanks, alkali chamber feed tanks and salt chamber feed tanks through emulsion tubes through an electrode chamber peristaltic pump, an acid chamber feed peristaltic pump, an alkali chamber feed peristaltic pump and a salt chamber feed peristaltic pump to form four independent solution channels of an electrode chamber, an acid chamber, an alkali chamber and a salt chamber, and the anode electrode 11 and the cathode electrode 10 of the bipolar membrane device are respectively connected with matched electrodes through leadsThe positive electrode 9a and the negative electrode 9b of the electronic load 9 are connected.

The bipolar membrane-based power generation device for power generation comprises the following steps:

500mL of a solution with a molar concentration of 0.10mol/L K was poured into the electrode chamber pot₃[Fe(CN)₆]、0.10mol/L K₄[Fe(CN)₆]And 0.25mol/L NaCl, the volume of the electrode liquid in the electrode chamber tank accounts for 50% of the volume of the electrode chamber tank, and the flow rate of the peristaltic pump of the electrode chamber is adjusted to be 150 mL/min.

And (3) pouring 14L of hydrochloric acid solution with the molar concentration of 0.3mol/L into the acid chamber feeding tank, wherein the volume of the acid solution in the acid chamber feeding tank accounts for 90% of the volume of the acid chamber feeding tank, and the flow rate of the acid chamber peristaltic pump is adjusted to be 40 mL/min.

And (3) pouring 14L of sodium hydroxide solution with the molar concentration of 0.3mol/L into the alkali chamber feeding tank, wherein the volume of alkali liquor in the alkali chamber feeding tank accounts for 90% of the volume of the alkali chamber feeding tank, and the flow rate of the alkali chamber peristaltic pump is adjusted to be 40 mL/min.

And (3) pouring 14L of sodium chloride solution with the molar concentration of 0.03mol/L into the salt chamber feeding tank, wherein the volume of the salt liquid in the salt chamber feeding tank accounts for 90% of the volume of the salt chamber feeding tank, and the flow rate of the salt chamber peristaltic pump is adjusted to be 40 mL/min.

And opening the acid chamber feeding peristaltic pump, the alkali chamber feeding peristaltic pump, the salt chamber feeding peristaltic pump and the electrode chamber peristaltic pump to enable the solution in the acid chamber feeding tank, the alkali chamber feeding tank, the salt chamber feeding tank and the electrode chamber tank to continuously flow to remove air bubbles in the device.

And the solutions in the acid chamber feeding tank, the alkali chamber feeding tank, the salt chamber feeding tank and the electrode chamber tank continuously flow for 7min and then are connected with an electronic load.

This example tests the stack Open Circuit Voltage (OCV), stack resistance (R) and maximum power (P) during power generation_max) The test results are shown in table 1.

Example 2:

the bipolar membrane-based power generation device shown in example 1 is used for power generation, and comprises the following steps:

This example tests the stack Open Circuit Voltage (OCV), stack resistance (R) and maximum power (P) during power generation_max) The test results are shown in table 1.

Example 3:

the bipolar membrane-based power generation device shown in example 1 is used for power generation, and comprises the following steps:

This example tests the stack Open Circuit Voltage (OCV), stack resistance (R) and maximum power (P) during power generation_max) The test results are shown in table 1.

Example 4:

the bipolar membrane-based power generation device shown in example 1 is used for power generation, and comprises the following steps:

This example tests the stack Open Circuit Voltage (OCV), stack resistance (R) and maximum power (P) during power generation_max) The test results are shown in table 1.

Example 5:

the bipolar membrane-based power generation device shown in example 1 is used for power generation, and comprises the following steps:

In the present example, the Open Circuit Voltage (OCV), the resistance (R) and the maximum power (Pmax) of the stack were measured during the power generation, and the results are shown in table 1.

FIG. 5 is a graph showing the open circuit voltage of the membrane stack as a function of flow rate according to examples 1 to 5 of the present invention.

Example 6:

generating electricity using the bipolar membrane based power plant shown in example 1, wherein the bipolar membrane was replaced with a commercially available inlet membrane, comprising the steps of:

And (3) pouring 14L of sodium chloride solution with the molar concentration of 0.03mol/L into the salt chamber feeding tank, wherein the volume of the salt liquid in the salt chamber feeding tank accounts for 90% of the volume of the salt chamber feeding tank, and adjusting the flow rate of the salt chamber peristaltic pump to be 40 mL/min.

In the present example, the Open Circuit Voltage (OCV), the resistance (R) and the maximum power (Pmax) of the stack were measured during the power generation, and the results are shown in table 1.

Example 7:

And (3) pouring 14L of sodium chloride solution with the molar concentration of 0.03mol/L into the salt chamber feeding tank, wherein the volume of the salt liquid in the salt chamber feeding tank accounts for 90% of the volume of the salt chamber feeding tank, and adjusting the flow rate of a salt chamber peristaltic pump to be 50 mL/min.

This example tested membrane stack opening during power generationCircuit Voltage (OCV), stack resistance (R) and maximum power (P)_max) The test results are shown in table 1.

Example 8:

And (3) pouring 14L of sodium chloride solution with the molar concentration of 0.03mol/L into the salt chamber feeding tank, wherein the volume of the salt liquid in the salt chamber feeding tank accounts for 90% of the volume of the salt chamber feeding tank, and adjusting the flow rate of a salt chamber peristaltic pump to be 60 mL/min.

This example tests the stack Open Circuit Voltage (OCV), stack resistance (R) and maximum power (P) during power generation_max) The test results are shown in table 1.

FIG. 6 is a graph showing the open circuit voltage of the membrane stack as a function of flow rate according to examples 6-8 of the present invention;

example 9:

And (3) pouring 14L of hydrochloric acid solution with the molar concentration of 0.5mol/L into the acid chamber feeding tank, wherein the volume of the acid solution in the acid chamber feeding tank accounts for 90% of the volume of the acid chamber feeding tank, and the flow rate of the acid chamber peristaltic pump is adjusted to be 50 mL/min.

And (3) pouring 14L of sodium hydroxide solution with the molar concentration of 0.5mol/L into the alkali chamber feeding tank, wherein the volume of alkali liquor in the alkali chamber feeding tank accounts for 90% of the volume of the alkali chamber feeding tank, and the flow rate of the alkali chamber peristaltic pump is adjusted to be 50 mL/min.

And (3) pouring 14L of sodium chloride solution with the molar concentration of 0.03mol/L into the salt chamber feeding tank, wherein the volume of the salt liquid in the salt chamber feeding tank accounts for 90% of the volume of the salt chamber feeding tank, and adjusting the flow rate of a salt chamber peristaltic pump to be 50 mL/min.

This example tests the stack Open Circuit Voltage (OCV), stack resistance (R) and maximum power (P) during power generation_max) The test results are shown in table 1.

Example 10:

And (3) pouring 14L of hydrochloric acid solution with the molar concentration of 0.9mol/L into the acid chamber feeding tank, wherein the volume of the acid solution in the acid chamber feeding tank accounts for 90% of the volume of the acid chamber feeding tank, and the flow rate of the acid chamber peristaltic pump is adjusted to be 50 mL/min.

And (3) pouring 14L of sodium hydroxide solution with the molar concentration of 0.9mol/L into the alkali chamber feeding tank, wherein the volume of alkali liquor in the alkali chamber feeding tank accounts for 90% of the volume of the alkali chamber feeding tank, and the flow rate of the alkali chamber peristaltic pump is adjusted to be 50 mL/min.

And (3) pouring 14L of sodium chloride solution with the molar concentration of 0.03mol/L into the salt chamber feeding tank, wherein the volume of the salt liquid in the salt chamber feeding tank accounts for 90% of the volume of the salt chamber feeding tank, and adjusting the flow rate of a salt chamber peristaltic pump to be 50 mL/min.

This example tests the stack Open Circuit Voltage (OCV), stack resistance (R) and maximum power (P) during power generation_max) The test results are shown in table 1.

Example 11:

And (3) pouring 14L of hydrochloric acid solution with the molar concentration of 1.1mol/L into the acid chamber feeding tank, wherein the volume of the acid solution in the acid chamber feeding tank accounts for 90% of the volume of the acid chamber feeding tank, and the flow rate of the acid chamber peristaltic pump is adjusted to be 50 mL/min.

And (3) pouring 14L of sodium hydroxide solution with the molar concentration of 1.1mol/L into the alkali chamber feeding tank, wherein the volume of alkali liquor in the alkali chamber feeding tank accounts for 90% of the volume of the alkali chamber feeding tank, and the flow rate of the alkali chamber peristaltic pump is adjusted to be 50 mL/min.

And (3) pouring 14L of sodium chloride solution with the molar concentration of 0.03mol/L into the salt chamber feeding tank, wherein the volume of the salt liquid in the salt chamber feeding tank accounts for 90% of the volume of the salt chamber feeding tank, and adjusting the flow rate of a salt chamber peristaltic pump to be 50 mL/min.

This example tests the stack Open Circuit Voltage (OCV), stack resistance (R) and maximum power (P) during power generation_max) The test results are shown in table 1.

FIG. 7 is a graph showing the open circuit voltage of the membrane stack as a function of concentration for examples 9 to 11 of the present invention.

Table 1 open circuit voltage, stack resistance and maximum power of the stacks of examples 1 to 11 of the present invention

	OCV/V	R/Ω	P_max/W
				Example 1	3.773	2.294	1.4063
Example 2	3.853	2.253	1.4520
				Example 3	3.913	2.513	1.3955
Example 4	4.107	2.601	1.3600
				Example 5	4.103	2.868	1.2640
Example 6	4.106	1.486	2.3353
				Example 7	4.113	1.435	2.3757
Example 8	4.120	1.602	2.3257
				Example 9	4.303	1.369	2.6083
Example 10	4.360	1.556	2.5827
				Example 11	4.427	1.315	2.8213

In summary, compared with the prior art, the method has the following beneficial effects:

in the embodiment of the invention, a cathode electrode and an anode electrode are respectively arranged on two sides of a bipolar membrane stack, the bipolar membrane stack at least comprises a repeating unit, and a first cation exchange membrane, a first separation net, a bipolar membrane, a second separation net, an anion exchange membrane, a third separation net and a second cation exchange membrane are sequentially laminated in the direction from the anode electrode to the cathode electrode in the repeating unit, and five compartments of an anode compartment, an alkali compartment, an acid compartment, a salt compartment and a cathode compartment are correspondingly formed; the bipolar membrane stack is introduced on the basis of the reverse electrodialysis technology to form reverse bipolar membrane electrodialysis, acid and alkali pass through an acid chamber and an alkali chamber on two sides of a bipolar membrane respectively, and hydrogen ions and hydroxide ions in the acid and the alkali permeate through a cation exchange layer and an anion exchange layer of the bipolar membrane respectively to generate water through neutralization reaction on a bipolar membrane middle layer, so that two gradients are generated on the bipolar membrane: the pH gradient and the salinity gradient generated by different compositions of the acidic solution and the alkaline solution, thereby realizing the effective conversion of the chemical energy of the acidic solution and the alkaline solution into the electric energy; the whole process can be carried out at normal temperature, the raw materials are wide in source and low in price, the energy density is high, the theoretical membrane stack voltage is high, the generated energy can be flexibly adjusted, and the safety performance is high.

It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.

The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

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