阅读说明：本技术 三隔室铁铝液流电池 (Three-compartment iron-aluminum flow battery ) 是由 郑志海 于 2020-12-25 设计创作，主要内容包括：本发明铁铝液流电池,属于化学储能领域,特别是液流电池技术领域,具体的涉及一种铁铝液流电池。包括至少一个单电池,单电池包括阳极板、阳极反应室、阴隔膜、催化反应室、阳隔膜、阴极反应室、阴极板,在阳极和阴隔膜之间的阳极反应室通入阳极电解液,于阴隔膜及阳隔膜之间的催化反应室通入催化液,于阴极和阳隔膜之间通入阴极电解液,阴极电解液是去离子水、铝化合物、铝粉的混合物,催化液是去离子水、氯化钾、氯化钠的混合物、阳极电解液是去离子水、铁化合物的混合物,阳隔膜为阳离子交换膜、阴隔膜为阴离子交换膜。本发明所述的铁铝液流电池,具有低造价、无毒、低腐蚀、不易燃,不爆炸、无放热反应、循环充放电周期短、无自放电的优点。(The invention relates to an iron-aluminum flow battery, belongs to the field of chemical energy storage, particularly relates to the technical field of flow batteries, and particularly relates to an iron-aluminum flow battery. The single cell comprises an anode plate, an anode reaction chamber, an anion diaphragm, a catalytic reaction chamber, an anode diaphragm, a cathode reaction chamber and a cathode plate, wherein an anode electrolyte is introduced into the anode reaction chamber between the anode and the anion diaphragm, a catalytic liquid is introduced into the catalytic reaction chamber between the anion diaphragm and the anode diaphragm, a cathode electrolyte is introduced between the cathode and the anode diaphragm, the cathode electrolyte is a mixture of deionized water, an aluminum compound and aluminum powder, the catalytic liquid is a mixture of deionized water, potassium chloride and sodium chloride, the anode electrolyte is a mixture of deionized water and an iron compound, the anode diaphragm is a cation exchange membrane, and the cathode diaphragm is an anion exchange membrane. The iron-aluminum flow battery has the advantages of low manufacturing cost, no toxicity, low corrosion, no flammability, no explosion, no exothermic reaction, short cycle charge-discharge period and no self-discharge.)

1. The three-compartment iron-aluminum flow battery is characterized by consisting of a pile formed by a plurality of single cells, wherein the single cells sequentially comprise an anode plate (1), an anode reaction chamber (2), a cathode diaphragm (3), a catalytic reaction chamber (4), an anode diaphragm (5), a cathode reaction chamber (6) and a cathode plate (7), sealing partition plates (8) are arranged at two ends of the cathode reaction chamber (6), the catalytic reaction chamber (4) and the anode reaction chamber (2), an anolyte is introduced into the anode reaction chamber (2), a catalytic liquid is introduced into the catalytic reaction chamber (4), a catholyte is introduced into the cathode reaction chamber (6), the catholyte is a mixture of deionized water, an aluminum compound and aluminum powder, the catalytic liquid is a mixture of deionized water, ammonium chloride and sodium chloride, and the anolyte is a mixture of deionized water, iron powder and an iron compound, the positive diaphragm is a cation exchange membrane, and the negative diaphragm is an anion exchange membrane.

2. The three-compartment iron-aluminum flow battery of claim 1, wherein the deionized water in the catholyte, catalytic solution, and anolyte meets the following criteria: pH6.0-8.0, conductivity < 0.6ms/cm, total soluble solid content < 300ppm, K⁺＜ 10ppm，Ca＜1ppm，Na⁺＜10ppm，Mg²⁺＜20ppm，F＜2ppm，SO₄ ^2-＜100ppm，Cl ^-＜15ppm。

3. The three-compartment iron-aluminum flow battery of claim 1, wherein the aluminum compound in the catholyte is aluminum chloride, the aluminum powder having a particle size of 1-10 μm; the aluminum chloride accounts for 2-10% of the total mass of the deionized water, the aluminum powder accounts for 5-20% of the total mass of the deionized water, and the balance is the deionized water.

4. The three-compartment iron-aluminum flow battery of claim 1, wherein the iron compound in the anolyte is a mixture of ferric chloride and ferrous chloride; 1-2% of the total mass of ferrous chloride deionized water, 1-3% of the total mass of ferric chloride deionized water, 3-7% of the total mass of iron powder deionized water and the balance of deionized water.

5. The three-compartment iron-aluminum flow battery of claim 1, wherein the catalytic liquid is formed by mixing deionized water, ammonium chloride and sodium chloride, and the mass ratio of the deionized water to the ammonium chloride to the sodium chloride is as follows: ammonium chloride: sodium chloride =1:0.5: 0.5.

6. A three-compartment iron-aluminum flow battery according to claim 1, characterized in that the anode plate (1) is any one of a graphite plate, an inert metal plate or a carbon cloth; the cathode plate (7) is any one of an aluminum plate and an aluminum composite plate.

7. The three-compartment ferroaluminum flow battery of claim 1, wherein the catholyte and the catalytic solution are neutral electrolytes having a PH of 6.0 to 8.0.

8. The three-compartment iron-aluminum flow battery of claim 1, wherein the anolyte is a weakly acidic electrolyte having a PH of 2.0-6.0.

9. A three-compartment iron-aluminum flow battery of claim 1,

the anolyte was prepared using the following method:

1) adding deionized water with the formula amount into a mixing container at normal temperature;

2) adding solid ferric chloride with the formula amount into a mixing container, and stirring and dissolving until the mixture is uniformly mixed and has no precipitate;

3) adding solid ferrous chloride in a formula amount into a mixing container, and stirring and dissolving until the mixture is uniformly mixed without precipitates;

4) adding iron powder with an amount not in a formula amount into a mixing container, and stirring and mixing to form a suspension to prepare an anolyte;

the catholyte was prepared using the following method:

1) adding deionized water with the formula amount into a mixing container at normal temperature;

2) adding solid aluminum chloride in a formula amount into a mixing container, and stirring and dissolving until the mixture is uniformly mixed without precipitates;

3) adding the aluminum powder with the formula amount into a mixing container, stirring and mixing to form an aluminum chloride/aluminum powder suspension, and preparing the cathode electrolyte.

Technical Field

The invention belongs to the technical field of flow batteries, and particularly relates to a three-compartment iron-aluminum flow battery.

Background

With the increasing living standard and the fierce demand for energy, the traditional fossil energy will gradually fail, and the demand for energy of people cannot be met in the near future. Therefore, development and utilization of renewable energy such as wind energy and solar energy are receiving much attention. However, an effective way to efficiently utilize the discontinuous, unstable and regional environment-limited renewable energy is an energy storage technology, and a good energy storage technology is a key technology for developing and utilizing new energy. The flow battery has independent output power and capacity, so that the system design is flexible; the energy efficiency is high, the service life is long, the operation stability and reliability are high, and the self-discharge is low; the method has the advantages of large site selection freedom degree, no pollution, simple maintenance, low operation cost, high safety and the like, has wide development prospect in the aspect of large-scale energy storage, is considered as an effective method for solving the randomness and intermittent unsteady state characteristics of a solar energy power generation system, a wind energy power generation system and other renewable energy power generation systems, and has important requirements in the construction of renewable energy power generation and an intelligent power grid.

Currently, the developed flow battery systems include all-vanadium flow batteries, zinc-nickel flow batteries, sodium polysulfide-bromine flow batteries, and the like, but the main limitations restricting the commercialization of the existing flow batteries are the defects of high cost, low energy density, and the like. The all-vanadium redox flow battery is toxic and acidic, the stability of the electrolyte is poor, and the cost of raw materials is high. The sodium polysulfide bromine flow battery is toxic, acidic, has limited cycle charge and discharge times and poor thermal stability, and a cooling system must be configured. The zinc-nickel flow battery needs strong alkali as a supporting electrolyte, and the high-concentration alkali solution seriously corrodes equipment, so that the high-efficiency, cheap, safe and reliable storage and release of energy cannot be realized. Two ways are mainly used for reducing the cost of the flow battery, namely reducing the cost of key materials such as electrodes, membranes, bipolar plates and the like; firstly, the energy density of the battery is improved, and the cost of the whole system is reduced. And moreover, the improvement of the energy density can also reduce the weight, the occupied area and the space of the energy storage system, improve the environmental adaptability and the mobility of the system and expand the application field of the flow battery.

Disclosure of Invention

Aiming at the problems in the prior art, the invention aims to provide a three-compartment iron-aluminum flow battery which has the advantages of environmental protection, no toxicity, low corrosion, long service life, no explosion, high-frequency and high-power cyclic charge and discharge, good thermal stability, zero capacity attenuation and service life of more than 30 years.

The invention is realized by the following technical scheme:

the three-compartment iron-aluminum flow battery is characterized by comprising a galvanic pile formed by a plurality of single cells, wherein the single cells sequentially comprise an anode plate, an anode reaction chamber, a cathode diaphragm, a catalytic reaction chamber, an anode diaphragm, a cathode reaction chamber and a cathode plate, sealing clapboards are arranged at two ends of the cathode reaction chamber, the catalytic reaction chamber and the anode reaction chamber, anode electrolyte is introduced into the anode reaction chamber, catalytic liquid is introduced into the catalytic reaction chamber, cathode electrolyte is introduced into the cathode reaction chamber, the cathode electrolyte is a mixture of deionized water, aluminum compound and aluminum powder, the catalytic liquid is a mixture of deionized water, potassium chloride and sodium chloride, the anode electrolyte is a mixture of deionized water, iron powder and iron compound, the anode diaphragm is a cation exchange membrane, and the cathode diaphragm is an anion exchange membrane.

Preferably, the deionized water in the catholyte, the catalytic solution and the anolyte meets the following indexes: pH6.0-8.0, conductivity < 0.6ms/cm, total soluble solid content < 300ppm, K⁺＜ 10ppm，Ca＜1ppm，Na⁺＜10ppm，Mg²⁺＜20ppm，F＜2ppm，SO₄ ^2-＜100ppm，Cl ^-＜15ppm。

Preferably, the aluminum compound in the catholyte is aluminum chloride, and the particle size of the aluminum powder is 1-10 μm; the aluminum chloride accounts for 2-10% of the total mass of the deionized water, the aluminum powder accounts for 5-20% of the total mass of the deionized water, and the balance is the deionized water.

Preferably, the iron compound in the anolyte is a mixture of ferric chloride and ferrous chloride; ferrous chloride accounts for 1-2% of the total mass of the deionized water, ferric chloride accounts for 1-3% of the total mass of the deionized water, iron powder accounts for 3-7% of the total mass of the deionized water, and the balance is the deionized water.

Preferably, the catalytic liquid is prepared by mixing deionized water, ammonium chloride and sodium chloride, and the mass ratio of the deionized water to the ammonium chloride to the sodium chloride is as follows: ammonium chloride: sodium chloride =1:0.5: 0.5.

Preferably, the anode plate is any one of a graphite plate, an inert metal plate or a carbon cloth; the cathode plate is any one of an aluminum plate and an aluminum composite plate.

Preferably, the catholyte and the catalytic liquid are neutral electrolytes, and the pH value of the neutral electrolytes is 6.0-8.0.

Preferably, the anolyte is a weakly acidic electrolyte having a pH of 2.0 to 6.0.

Preferably, the anolyte is prepared using the following method: 1) adding deionized water with the formula amount into a mixing container at normal temperature; 2) adding solid ferric chloride with the formula amount into a mixing container, and stirring and dissolving until the mixture is uniformly mixed and has no precipitate; 3) adding solid ferrous chloride in a formula amount into a mixing container, and stirring and dissolving until the mixture is uniformly mixed without precipitates; 4) adding iron powder with an amount not in a formula amount into a mixing container, and stirring and mixing to form a suspension to prepare an anolyte;

the catholyte was prepared using the following method: 1) adding deionized water with the formula amount into a mixing container at normal temperature; 2) adding solid aluminum chloride with the formula amount into a mixing container, and stirring for dissolving; 3) adding the aluminum powder with the formula amount into a mixing container, stirring and mixing to form aluminum chloride/aluminum powder suspension for later use.

The iron-aluminum flow battery can realize miniaturization, and can be widely applied to the fields of power grid energy storage peak regulation, wind power photovoltaic energy storage, electric automobile field, renewable energy source and the like; compared with a vanadium redox flow battery, the cost is greatly reduced, the volume and the weight are both greatly reduced, the large scale can be realized, and the environment is protected without pollution.

The core reaction mechanism of the invention is that compared with the conventional flow battery, the invention adds a catalytic reaction chamber, and the ion exchange of the catalytic reaction chamber is communicated with the circuit of the battery and isolates the generation of adverse reaction. While allowing some half-cells that would otherwise not react in the conventional manner to react.

Drawings

FIG. 1 is a schematic diagram of a cell structure according to the present invention;

FIG. 2 is a diagram of a discharge test circuit according to the present invention;

FIG. 3 is a diagram of a charge test circuit according to the present invention;

in the figure, 1-anode plate, 2-anode reaction chamber, 3-cathode diaphragm, 4-catalytic reaction chamber, 5-anode diaphragm, 6-cathode reaction chamber, 7-cathode plate and 8-sealing separator.

Detailed Description

The technical scheme of the invention is further described in detail and specific examples are given in the following with reference to the attached drawings of the specification.

The invention relates to a three-compartment iron-aluminum flow battery, which consists of a pile formed by a plurality of single cells, wherein the single cells have the specific structure shown in figure 1 and sequentially comprise an anode plate, an anode reaction chamber, a cathode diaphragm, a catalytic reaction chamber, an anode diaphragm, a cathode reaction chamber and a cathode plate, sealing clapboards are arranged at two ends of the cathode reaction chamber, the catalytic reaction chamber and the anode reaction chamber, an anode electrolyte is introduced into the anode reaction chamber, a catalytic liquid is introduced into the catalytic reaction chamber, a cathode electrolyte is introduced into the cathode reaction chamber, the cathode electrolyte is a mixture of deionized water, an aluminum compound and aluminum powder, the catalytic liquid is a mixture of the deionized water, ammonium chloride and sodium chloride, the anode electrolyte is a mixture of the deionized water, the iron compound and iron powder, and the anode diaphragm is a cation exchange membrane and. The anode plate is any one of a graphite plate, an inert metal plate or carbon cloth; the cathode plate is any one of an aluminum plate and an aluminum composite plate. The cathode electrolyte and the catalytic liquid are neutral electrolytes with the pH value of 6.0-8.0, and the anode electrolyte is weak-acid electrolyte with the pH value of 2.0-6.0.

The deionized water in the catholyte, the catalytic solution and the anolyte conforms to the following indexes: pH6.0-8.0, conductivity < 0.6ms/cm, total soluble solid content < 300ppm, K⁺＜ 10ppm，Ca＜1ppm，Na⁺＜10ppm，Mg²⁺＜20ppm，F＜2ppm，SO₄ ^2-＜100ppm，Cl ^-Less than 15 ppm. The aluminum compound in the cathode electrolyte is aluminum chloride, and the particle size of the aluminum powder is 1-10 mu m; the aluminum chloride accounts for 2-10% of the total mass of the deionized water, the aluminum powder accounts for 5-20% of the total mass of the deionized water, and the balance is the deionized water. The iron compound in the anolyte is a mixture of ferric chloride and ferrous chloride; ferrous chloride accounts for 1-2% of the total mass of the deionized water, ferric chloride accounts for 1-3% of the total mass of the deionized water, iron powder accounts for 3-7% of the total mass of the deionized water, and the balance is the deionized water. The catalytic liquid is formed by mixing deionized water, ammonium chloride and sodium chloride, and the mass ratio of the deionized water to the ammonium chloride to the sodium chloride is as follows: ammonium chloride: sodium chloride =1:0.5: 0.5.

The anolyte was prepared using the following method: 1) adding deionized water with the formula amount into a mixing container at normal temperature; 2) adding solid ferric chloride with the formula amount into a mixing container, and stirring and dissolving until the mixture is uniformly mixed and has no precipitate; 3) adding solid ferrous chloride in a formula amount into a mixing container, and stirring and dissolving until the mixture is uniformly mixed without precipitates; 4) adding iron powder with an amount not in a formula amount into a mixing container, and stirring and mixing to form a suspension to prepare an anolyte; the catholyte was prepared using the following method: 1) adding deionized water with the formula amount into a mixing container at normal temperature; 2) adding solid aluminum chloride in a formula amount into a mixing container, and stirring and dissolving until the mixture is uniformly mixed without precipitates; 3) adding the aluminum powder with the formula amount into a mixing container, stirring and mixing to form an aluminum chloride/aluminum powder suspension, and preparing the cathode electrolyte.

Example 1

An iron-aluminum flow battery is composed of 1 galvanic pile, each galvanic pile contains 10 monocells, each monocell comprises an anode plate, a cathode diaphragm, an anode diaphragm and a cathode plate, an anolyte is introduced between the anode and the cathode diaphragms, a catholyte is introduced between the cathode and the cathode diaphragms, and a catalytic liquid is introduced between the anode diaphragm and the cathode diaphragm. The anolyte is a mixture of deionized water, ferric chloride, ferrous chloride and iron powder, wherein the ferric chloride accounts for 2% of the total mass of the deionized water, the ferrous chloride accounts for 1% of the total mass of the deionized water, the iron powder accounts for 5% of the total mass of the deionized water, and the balance is the deionized water; the cathode electrolyte is a mixture of deionized water, aluminum trichloride and aluminum powder, wherein the aluminum powder accounts for 10% of the total mass of the deionized water, the aluminum chloride accounts for 5% of the total mass of the deionized water, the balance is the deionized water, the catalytic liquid is formed by mixing the deionized water, ammonium chloride and sodium chloride, and the mass ratio of the deionized water to the aluminum chloride is as follows: ammonium chloride: sodium chloride =1:0.5:0.5, and the membrane is an anionic membrane or a cationic membrane. Effective area of the diaphragm is 0.018m²And the effective volume of the reaction chamber is 36 ml. The anode plate is made of carbon fiber cloth, the cathode plate is made of pure aluminum foil, the anode diaphragm is a cation exchange membrane, and the cathode diaphragm is an anion exchange membrane.

Wherein, the deionized water meets the following indexes: pH6.0-8.0, conductivity < 0.6ms/cm, total soluble solid content < 300ppm, K⁺＜ 10ppm，Ca＜1ppm，Na⁺＜10ppm，Mg²⁺＜20ppm，F＜2ppm，SO₄ ^2-＜100ppm，Cl ^-＜15ppm。

The preparation method of the anolyte comprises the following steps: (1) adding 1000kg of deionized water into a mixing container at normal temperature; (2) solid ferric trichloride FeCl₃Adding 20kg of the mixture into a mixing container, stirring and dissolving; (3) after ferric trichloride is completely dissolved, solid ferrous chloride FeCl is added₂10kg of the mixture is added into a mixing container to be stirred and dissolved; and (4) after the ferrous chloride is completely dissolved, adding 50kg of iron powder into a mixing container, and stirring and mixing to form a suspension for later use.

The preparation method of the cathode electrolyte comprises the following steps: (1) firstly, 1000kg of deionized water is added into a mixing container; (2) then the solid AlCl is added₃Adding 50kg of the mixture into a mixing container, stirring and dissolving; (3) after the aluminum trichloride is completely dissolved, 100kg of solid aluminum powder is added into a mixing container to be stirred and mixed to form a suspension for later use.

The preparation method of the catalytic liquid comprises the following steps: (1) firstly, 1000kg of deionized water is added into a mixing container; (2) then adding 500kg of solid sodium chloride into a mixing container, stirring and dissolving; (3) after the sodium chloride is completely dissolved, 500kg of ammonium chloride is added into a mixing container to be stirred and mixed to form a catalytic liquid for standby.

Example 2

The utility model provides an iron-aluminum redox flow battery, comprises 1 electric pile, contains 10 monocells in every electric pile, and the monocell includes anode plate, negative diaphragm, positive diaphragm, negative plate, and carbon fiber cloth is selected for use to the anode plate, and pure aluminium foil is selected for use to the negative plate, lets in anolyte between positive pole and positive diaphragm, lets in catholyte between negative pole and negative diaphragm, lets in catalytic liquid between positive diaphragm and negative diaphragm. The anolyte is a mixture of deionized water, ferric chloride, ferrous chloride and iron powder, wherein the iron powder accounts for 6% of the total mass of the deionized water, the ferric chloride accounts for 3% of the total mass of the deionized water, the ferrous chloride accounts for 2% of the total mass of the deionized water, and the balance is the deionized water; the cathode electrolyte is a mixture of deionized water, aluminum trichloride and aluminum powder, wherein the aluminum powder in the cathode electrolyte accounts for 15% of the total mass of the deionized water, the aluminum chloride accounts for 3% of the total mass of the deionized water, and the balance is the deionized water; the catalytic liquid is a mixture of deionized water, sodium chloride and ammonium chloride according to the mass ratio of 1:0.5:0.5, the diaphragm is an anion membrane and a cation membrane,

wherein, the deionized water used in the catholyte and the anolyte conforms to the following indexes: pH6.0-8.0, conductivity < 0.6ms/cm, total soluble solid content < 300ppm, K⁺＜ 10ppm，Ca＜1ppm，Na⁺＜10ppm，Mg²⁺＜20ppm，F＜2ppm，SO₄ ^2-＜100ppm，Cl ^-＜15ppm。

The preparation method of the anolyte comprises the following steps: (1) adding 1000kg of deionized water into a mixing container at normal temperature; (2) solid ferric trichloride FeCl₃Adding 30kg of the mixture into a mixing container, stirring and dissolving; (3) after ferric trichloride is completely dissolved, solid ferrous chloride FeCl is added₂Adding 20kg of the mixture into a mixing container, stirring and dissolving; (4) after the ferrous chloride is completely dissolved, 60kg of iron powder is added into a mixing container and stirred and mixed to form a suspension for later use.

The preparation method of the cathode electrolyte comprises the following steps: (1) firstly, 1000kg of deionized water is added into a mixing container; (2) then the solid AlCl is added₃Adding 30kg of the mixture into a mixing container, stirring and dissolving; (3) after aluminum trichloride is completely dissolved, 150kg of solid aluminum powder is added into a mixing container and stirred and mixed to form a suspension for later use.

The preparation method of the catalyst solution was the same as in example 1.

The performance test of the iron-aluminum flow battery of the example 1 is carried out, and a discharge test circuit diagram is shown in fig. 2. The open-circuit voltage is 12.2V, and the load resistance is 1000W/150 omega. The discharge current was 81.2 mA. After 24 hours, the discharge current was 80 mA. Short-circuit discharge current 48A. When the voltage is discharged to the terminal voltage of 10V, the test is stopped.

The charging test circuit diagram is shown in FIG. 3, the charging voltage is 15V, and the charging current is 150 mA.

Reaction process of the catalytic reaction chamber:

and (3) discharging: na in the catalytic reaction chamber⁺Ions enter the anode reaction chamber through the anode diaphragm to participate in anode reaction, and Cl^-Ions enter the cathode reaction chamber through the anion diaphragm to participate in cathode reaction, and the ion concentration in the catalytic reaction chamber is reduced.

And (3) charging process: na in the anode reaction chamber⁺Ion passage through cation diaphragm catalytic reaction chamber, Cl in cathode reaction chamber^-Na which enters the catalytic reaction chamber from two sides respectively when the ionic cations enter the catalytic reaction chamber through the anion diaphragm⁺Ions, Cl^-The ion concentration of the catalytic reaction chamber is increased by synthesizing the sodium chloride solution by the ions.

Catholyte reaction equation:

discharging reaction: al-3 e^-+3Cl^-→AlCl₃

Charging reaction: al (Al)³⁺ +3e^--3Cl^-→ Al

Anolyte reaction equation:

discharging reaction: 3FeCl₃+3e^- +3Na⁺→3FeCl₂+3NaCl

Charging reaction: 3FeCl₂-3e^- +3NaCl-3Na⁺→3FeCl₃

The performance comparison results of the iron-aluminum flow battery of the invention and other batteries are shown in table 1.

TABLE 1 comparative table of performance of iron-aluminum flow battery and other batteries

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