CN105280943B - A kind of full manganese flow battery - Google Patents

Abstract

A kind of full manganese flow battery, battery module, electrolyte fluid reservoir, circulating pump, the circulation line that battery is formed by a section monocell or two section above cells in series form；Monocell includes positive pole, negative pole, and positive pole and negative pole are oppositely arranged, and space is left between positive pole and negative pole；Electrolyte is the aqueous solution containing divalent manganesetion, and positive pole and negative pole share electrolyte of the same race, and by circulating pump, electrolyte is circulated supply.The battery is reacted using deposition dissolving reaction, without barrier film due to both positive and negative polarity, it is only necessary to an electrolyte loop, overcomes the cross-contamination issue for passing flow battery, has the characteristics of having extended cycle life, cost is low, structure and manufacturing process are simple.

Description

An all-manganese flow battery

technical field

The invention relates to an all-manganese liquid flow battery, which can be widely used in the fields of electronics industry, transportation, mining and metallurgy, and the like.

Background technique

Since the industrial revolution, with the continuous growth of the global population and the continuous improvement of living standards, the demand for energy has also risen with the tide. However, the current energy structure dominated by fossil energy is obviously unable to support social development, so developing green and efficient renewable energy and increasing its proportion in the energy supply structure is an inevitable choice to achieve sustainable human development. As the main body of renewable energy: wind energy and solar energy are affected by the natural environment and geographical conditions such as day and night, season change, etc., and the electric energy output has the characteristics of fluctuation and discontinuity, which brings impact on the safe and stable operation of the power grid. The grid's ability to accommodate renewable energy power generation has become a key factor in determining its economic benefits and development prospects. To this end, researchers have proposed a solution for energy storage systems supporting renewable energy generation.

According to the principle and form of electric energy storage, the energy storage technologies currently proposed can be mainly divided into two categories: physical energy storage and chemical energy storage. Each energy storage technology has its own unique advantages and disadvantages. As a new type of electrochemical energy storage technology, flow energy storage battery has the advantages of safety, reliability, high charge and discharge efficiency, and long cycle life.

According to the redox pair of positive and negative electrodes, the currently proposed flow battery technologies mainly include: iron/chromium flow battery, all-vanadium flow battery, sodium polysulfide/bromine flow battery, zinc/cerium flow battery, zinc/cerium flow battery, etc. Bromine flow battery, etc. However, since the active materials of these systems are located in the positive and negative electrolytes respectively, and separated by ion exchange membranes, there are problems such as high battery production costs and cross-contamination of the positive and negative electrolytes. In 2004, Professor Pletcher of the United Kingdom first proposed the concept of a single-flow lead-acid battery. The electrolyte of this battery is lead methanesulfonate. When charging, divalent lead ions are oxidized to lead dioxide solid at the positive electrode and reduced to simple lead at the negative electrode. , a reversible reaction occurs upon discharge. There is no need for a diaphragm, which solves the problems of high cost and cross-contamination of electrolyte in traditional flow batteries. However, lead is toxic and will pollute the environment, so the battery has not been developed on a large scale, but it provides an effective way for researchers to solve the problems of high cost and cross-contamination of electrolyte in traditional flow batteries.

Contents of the invention

The present invention proposes the concept of an all-manganese single-flow battery by optimizing the oxidation-reduction pair of the positive and negative electrodes. In the electrolyte, there is no need for a diaphragm, which improves the problems of cross-contamination and high cost of traditional flow batteries. To achieve the above object, the specific technical solutions of the present invention are as follows:

An all-manganese flow battery is composed of a single battery or a battery module formed by connecting two or more single batteries in series, an electrolyte liquid storage tank, a circulation pump, and a circulation pipeline; the single battery includes a positive electrode, a negative electrode, a positive electrode and a negative electrode Relatively set, there is a gap between the positive electrode and the negative electrode;

The electrolyte liquid storage tank is filled with electrolyte, and the gap between the electrolyte liquid storage tank and the positive electrode and the negative electrode is connected through a circulation pipeline. The gap between the negative electrodes is then returned to the electrolyte storage tank; the electrolyte is an aqueous solution containing divalent manganese ions, the positive and negative electrodes share the same electrolyte, and the electrolyte is circulated and supplied through the circulating pump.

The positive electrode reaction is the liquid-solid phase conversion of divalent manganese ions and manganese dioxide; the negative electrode reaction is the liquid-solid phase conversion of divalent manganese ions and elemental manganese.

The active material containing manganese ions in the electrolyte is one or both of MnSO ₄ or Mn(NO ₃ ) ₂ , and the concentration range of the active material for manganese ions is 0.1mol dm ^-3 to 3mol dm ^-3 ;

A supporting electrolyte is also added to the electrolyte. The supporting electrolyte is one or two of H ₂ SO ₄ or HNO ₃ , and the concentration range of the supporting electrolyte is 0.05mol dm ^-3 to 3mol dm ^-3 ;

The electrolyte is also added or not added with an additive to improve the conductivity of the electrolyte. The additive is one or more of K ₂ SO ₄ , KNO ₃ , Na ₂ SO ₄ , and NaNO ₃ ; when the additive is added, the electrolyte The concentration range of the additive is 0.1moldm ^-3 ~ 3mol dm ^-3 .

The material of the positive electrode and the negative electrode is conductive metal or conductive carbon material.

The positive and negative poles are plate electrodes or porous electrodes.

Beneficial effects of the present invention:

This patent proposes the concept of an all-manganese single-flow battery through the optimization of the positive and negative electrode stacks. All substances are stored in the electrolyte in the state of ions, no diaphragm is needed, and only one electrolyte circuit is needed, which solves the problem of cross-contamination of traditional flow batteries. It has the characteristics of long cycle life, low cost, simple structure and manufacturing process.

Description of drawings

Figure 1 is a schematic diagram of a single cell of an all-manganese flow battery;

1. Positive terminal plate; 2. Negative terminal plate; 3. Positive pole; 4. Negative pole; 5. Pump; 6. Electrolyte storage tank;

Fig. 2 is a battery performance diagram of the all-manganese flow battery of the embodiment.

Detailed ways

Example

Electrolyte configuration:

Electrolyte: 40ml of electrolyte, which contains 1.0mol dm ^-3 MnSO ₄ , 1mol dm ^-3 K ₂ SO ₄ , 0.1moldm ^{- 3} H ₂ SO ₄ .

Battery Assembly:

The single cell is followed by the positive terminal plate, the positive 3x3cm ² nickel plate, the negative 3x3cm ² nickel plate, and the negative terminal plate. The single battery structure and system are shown in Figure 1.

Battery test:

Electrolyte flow rate: 5ml/min; charge and discharge current density 15mA/cm ² ; charge for 1h, discharge cut-off voltage is 0V. The performance of the battery is shown in Figure 2, and it can be seen from Figure 2 that the charge and discharge current density is 15mA/cm ² ; the charging time is 1h, and the average energy efficiency of the battery reaches about 75%.

Claims (3)

1. An all-manganese flow battery, characterized in that: the battery is composed of a single battery or a battery module formed by connecting two or more single batteries in series, an electrolyte liquid storage tank, a circulation pump, and a circulation pipeline; the single battery includes Positive and negative poles, the positive and negative poles are arranged opposite to each other, and there is a gap between the positive and negative poles; the positive and negative poles are conductive metal nickel; The electrolyte liquid storage tank is filled with electrolyte, and the gap between the electrolyte liquid storage tank and the positive electrode and the negative electrode is connected through a circulation pipeline. Return to the electrolyte storage tank after the gap between the negative electrodes; the electrolyte is an aqueous solution containing divalent manganese ions, the positive and negative electrodes share the same electrolyte, and the electrolyte is circulated and supplied through the circulation pump; The positive electrode reaction is the liquid-solid phase conversion of divalent manganese ions and manganese dioxide; the negative electrode reaction is the liquid-solid phase conversion of divalent manganese ions and elemental manganese. 2. The all-manganese flow battery according to claim 1, characterized in that: the manganese ion-containing active material in the electrolyte is one or both of MnSO ₄ or Mn(NO ₃ ) ₂ , and the manganese ion active material Concentration range 0.1mol dm ^-3 ～3mol dm ^-3 ; A supporting electrolyte is also added to the electrolyte. The supporting electrolyte is one or two of H ₂ SO ₄ or HNO ₃ , and the concentration range of the supporting electrolyte is 0.05mol dm ^-3 to 3mol dm ^-3 ; The electrolyte is also added or not added with an additive to improve the conductivity of the electrolyte. The additive is one or more of K ₂ SO ₄ , KNO ₃ , Na ₂ SO ₄ , and NaNO ₃ ; when the additive is added, the electrolyte The concentration range of the additive is 0.1mol dm ^-3 to 3mol dm ^-3 . 3. The all-manganese flow battery according to claim 1, characterized in that: the positive electrode and the negative electrode are plate electrodes or porous electrodes.