Water-soluble plumbic acid static storage battery

Abstract

The invention relates to a water-soluble plumbic acid static storage battery. The battery comprises a single battery body, the single battery body comprises an electrode plate, a static electrolyte and a container for containing the electrolyte, the electrode plate is inserted into the electrolyte, the electrolyte comprises water-soluble lead salt, acid, a lead dissolving agent and water, the lead dissolving agent can provide at least one water-soluble redox couple R oxidation and R reduction, and the water-soluble redox couple R oxidation and R reduction can be separated from the electrode plate. The electrode potential of the redox couple satisfies E [theta] (Pb < 2 + > / Pb) lt; e [theta] (R oxidation / R reduction) [lt]; e theta (PbO2 / Pb2 +). No diaphragm exists, the electrolyte is in a static state, facilities such as a circulating pump are not needed, lead ions are allowed to migrate under the concentration gradient effect, and meanwhile self-discharge caused by convection shuttling of the lead dissolving agent is greatly reduced. In the charging process, lead and lead dioxide can be flatly deposited on the surface of an electrode and can be completely dissolved in the discharging process, the cycling stability is good, the components can be kept stable for a long time, and the cost is low.

Description

Technical Field

[0001] The invention belongs to the technical field of electrochemical energy storage, and in particular relates to a water-soluble lead-acid static battery. Background Art

[0002] Lead-acid batteries have been used for hundreds of years since their introduction. Due to their safety, economy and reliability, they are still widely used. However, the production and recycling process of lead electrodes has the problem of heavy metal pollution, and the battery usually has a cycle life of only hundreds of cycles. Pletcher et al. proposed a water-soluble lead-acid flow battery, which uses nickel sheets and carbon plastic plates as electrodes, lead methanesulfonate and methanesulfonic acid as active substances and supporting electrolytes. During charging, lead methanesulfonate is deposited as lead element and lead dioxide at the negative electrode and positive electrode respectively, and dissolves and regenerates during discharge. Compared with traditional lead-acid batteries, its production and recycling process is simpler, less polluting, and has a higher utilization rate of lead; compared with conventional liquid flow batteries, it does not require a diaphragm and can adopt a single liquid flow structure, which greatly reduces the cost, so it has great development prospects. However, due to the side reaction of oxygen evolution at the positive electrode and the problem of powdering and shedding of the positive electrode active material at the end of discharge, the negative electrode lead element cannot be completely dissolved. After multiple cycles, the lead ion concentration in the electrolyte continues to decrease, resulting in capacity decay.

[0003] Patent CN110190312B discloses an electrolyte for lead flow batteries, which uses ferric nitrate or hexafluoroferric complex or ferric chloride as a catalyst to promote the redissolution of detached lead and lead dioxide into lead ions, thereby improving the cycle stability of the electrolyte. However, on the one hand, the scheme does not mention whether a diaphragm or other isolation facilities are set between the positive and negative electrodes. If there is no diaphragm and the iron concentration in the electrolyte reaches a level that can effectively dissolve solid lead (lead, lead dioxide), the ferric ions / ferrous ions shuttle back and forth between the positive and negative electrodes during the flow of the electrolyte, which is bound to cause self-discharge and reduce the current efficiency; if a diaphragm is used, it will increase the cost of the flow battery and easily cause the problem of lead dendrites being difficult to dissolve after falling off. On the other hand, the electrolyte of this scheme also contains fluoride ions, cobalt ions, nitrates and chloride ions. The presence of impurity ions will have a negative impact on the charging and discharging process: fluoride ions are easy to generate free hydrofluoric acid molecules in strong acidic solutions, and nitrates and chloride ions may participate in redox reactions and are not conducive to the electrodeposition of lead at the negative electrode. Although this battery solves the problem of lead dioxide dissolution to a certain extent, it causes problems such as self-discharge, and impurity ions will affect battery performance. Summary of the invention

[0004] In view of the above problems existing in the prior art, the present invention provides a water-soluble lead-acid static battery, which can avoid the self-discharge problem caused by the flow of electrolyte.

[0005] To achieve the above object, the technical solution provided by the present invention is as follows:

[0006] The present application provides a water-soluble lead-acid static storage battery, comprising a battery cell, wherein the battery cell comprises an electrode plate, an electrolyte in a static state and a container for holding the electrolyte, wherein the electrode plate is inserted in the electrolyte, wherein the electrolyte comprises a water-soluble lead salt, an acid, a lead dissolving agent and water, wherein the lead dissolving agent can provide at least one pair of water-soluble redox couples R 氧化 With R 还原 , the electrode potential of the redox couple satisfies E θ (Pb 2+ / Pb)< E θ (R 氧化 / R 还原 ) <E θ (PbO2 / Pb 2+ ).

[0007] Optionally, the battery is a battery stack composed of a group of battery cells or at least two groups of battery cells connected in series; when the battery is a battery stack composed of battery cells connected in series, the electrolytes between different battery cells are isolated.

[0008] Optionally, when the battery is a battery stack composed of battery cells connected in series, the electrode plates on both sides are used as the positive electrode and the negative electrode respectively, and the electrode plate between the positive electrode and the negative electrode is a bipolar plate, which is used to isolate the electrolyte phases between different battery cells.

[0009] Optionally, in a battery cell, the electrode plate includes a positive plate and a negative plate, the bottom end of the negative plate extends below the positive plate and / or the bottom end of the negative plate is connected to the bottom end of the positive plate through an isolation guide plate; the isolation guide plate is used to guide the active material detached from the positive plate to the negative plate of the same battery cell under the action of gravity. This design is also applicable to a battery stack obtained by connecting battery cells in series, in which the two adjacent plates with lower potential serve as negative plates and the plates with higher potential serve as positive plates.

[0010] The advantage of extending the bottom end of the negative electrode plate to below the positive electrode plate and / or connecting the bottom end of the negative electrode plate to the bottom end of the positive electrode plate through an isolation guide plate is that the lead dioxide shed from the positive electrode during discharge can reach the negative electrode by gravity sedimentation, which is beneficial to the reaction of active substances shed from the electrode into the electrolyte, eliminating the stirring or oscillating process, simplifying the operation steps and the required additional equipment.

[0011] Optionally, when the battery is a battery stack composed of battery cells connected in series, the positive electrode plate isolates the electrolytes between different battery cells, or the isolation guide plate and the positive electrode plate work together to isolate the electrolytes between different battery cells.

[0012] Optionally, the isolation guide plate has an angle of ≥45° with the horizontal direction.

[0013] Optionally, the shortest distance between the positive electrode plate and the negative electrode plate is 0.1-20 cm.

[0014] Optionally, the negative electrode is used as a container for holding electrolyte, and the positive electrode is immersed in the electrolyte in the container.

[0015] Optionally, the electrolyte is connected to the air.

[0016] Optionally, the lead dissolving agent includes one or more of water-soluble iron salts, ferrous salts, vanadium (V) salts, vanadium (IV) salts, and vanadium (III) salts.

[0017] In the lead-acid static battery of the present application, the water-soluble lead salt participates in the main battery reaction, and the acid serves as a supporting electrolyte and a conductive agent. The reaction formula is as follows:

[0018] positive electrode: (1)

[0019] negative electrode: (2)

[0020] Equation (1) and (2) are charging to the right and discharging to the left;

[0021] Since a small amount of lead dioxide will fall off the electrode during the positive electrode discharge process and cannot be discharged and dissolved, the lead dissolving agent can catalyze the discharge. The reaction formula is as follows:

[0022] Dissolved Lead Dioxide:

[0023] (3)

[0024] (4)

[0025] (5)

[0026] Dissolved lead:

[0027] (6)

[0028] (7)

[0029] (8)

[0030] Because the positive electrode will also produce oxygen during the charging and discharging process:

[0031] (9)

[0032] This reaction will cause the lead to be unable to dissolve completely. The electrolyte is connected to the outside air or the sealed air inside the battery. The lead dissolving agent reacts with the oxygen in the air to generate a high-valent lead dissolving agent. The reaction formula is as follows:

[0033] (10)

[0034] (11)

[0035] (12)

[0036] The generated high-valent lead dissolving agent participates in the above-mentioned reaction of dissolving the single lead in formula (6) to formula (8), which can accelerate the oxygen absorption and dissolution of the residual single lead in the negative electrode.

[0037] In the present application, no external force is required to be applied to the electrolyte. The electrolyte remains static and is exposed to an oxygen-containing environment. Lead ions migrate mainly by the concentration gradient between the electrode and the electrolyte, while the lead dissolving agent diffuses slowly due to the static electrolyte and the absence of a concentration gradient, thereby reducing self-discharge. The residual lead at the negative electrode promotes Fe 3+ The generated can also fully react and dissolve.

[0038] Optionally, the lead dissolving agent is one or more of methanesulfonate and fluoroborate.

[0039] Optionally, the electrode plate is one or more of conductive plastic, graphite, graphite felt, copper, nickel, and stainless steel.

[0040] Optionally, the water-soluble lead salt is one or more of lead methanesulfonate and lead fluoroborate; the acid is one or more of methanesulfonic acid and fluoroboric acid.

[0041] Optionally, the electrolyte includes the following components in concentrations: in mol / L, lead ions 0.05-3, hydrogen ions 0.001-8, iron ions 0-0.2, vanadium ions 0-0.2, methanesulfonate ions 0-8, and fluoroborate ions 0-8, wherein the concentrations of methanesulfonate and fluoroborate ions are not simultaneously 0, and the concentrations of iron and vanadium elements are not simultaneously 0.

[0042] Optionally, the electrolyte includes the following components in concentrations: in mol / L, lead ions 1.5-2, hydrogen ions 0.5-1, iron ions 0-0.2, vanadium ions 0-0.2, methanesulfonate ions 0-4, and fluoroborate ions 0-4, wherein the concentrations of methanesulfonate and fluoroborate ions are not simultaneously 0, and the concentrations of iron and vanadium ions are not simultaneously 0.

[0043] Optionally, a lead dendrite inhibitor is also included, which is one or more of methyl sulfate, methyl sulfonate, and fluoroborate of alkyl trimethylammonium, and the alkyl group is a straight chain with 12-22 carbon atoms.

[0044] Lead dendrites are easily generated at the negative electrode during charging, especially in the methanesulfonic acid system. The dendrites grow rapidly and easily contact the positive electrode, causing a short circuit. They are easy to fall off during discharge, so dendrite inhibitors are needed. Common additives for lead electroplating, such as emulsifier OP-10, can effectively inhibit the growth of dendrites, but are easily oxidized and decomposed by the lead dioxide at the positive electrode. Alkyl trimethylammonium salts have good chemical stability and can withstand the strong oxidizing properties of lead dioxide without decomposition in a strong acidic environment, and can inhibit the growth of lead dendrites.

[0045] Optionally, the lead dendrite inhibitor is methyl sulfate of alkyltrimethylammonium.

[0046] Optionally, the concentration of lead dendrite inhibitor in the electrolyte is 0-0.1 mol / L.

[0047] Optionally, the concentration of lead dendrite inhibitor in the electrolyte is 0-0.02 mol / L.

[0048] Compared with the prior art, this application has at least the following beneficial effects:

[0049] The present invention does not have a diaphragm, and the electrolyte is in a static state, and does not require facilities such as a circulating pump, allowing lead ions to migrate under the action of a concentration gradient, while greatly reducing the self-discharge caused by the convective shuttle of the lead dissolving agent (oxidized state / reduced state). During the charging process, lead and lead dioxide can be deposited evenly on the electrode surface, can be completely dissolved during the discharge process, have good cycle stability, and the components can remain stable for a long time, and have low cost; and the electrolyte does not contain harmful impurity ions.

[0050] The innovative design of the lead-acid static battery stack in the present invention isolates the electrolytes between different battery cells, thereby avoiding short circuits caused by the movement of part of the current along the electrolyte between the plates during charging and self-discharge caused by the potential difference of active materials between the electrolytes connected on both sides of the bipolar plates after charging is stopped.

[0051] In the present invention, the bottom end of the negative electrode plate is lower than the bottom end of the positive electrode plate, the bottom end of the negative electrode plate extends below the positive electrode plate and / or the bottom end of the negative electrode plate is connected to the bottom end of the positive electrode plate through an isolation guide plate; the active material detached from the positive electrode plate can be directly settled under the action of gravity or settled along the isolation guide plate to the surface of the negative electrode plate to be reduced, the electrolyte can be used for a long time under completely static conditions to maintain stable composition, and the battery efficiency is high. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 It is a schematic diagram of the structure of a series-connected battery stack of a conventional liquid flow battery in the prior art;

[0053] Figure 2 It is a static battery structure in which the electrode plates are arranged in parallel in the present invention, wherein a is a battery cell and b is a battery stack;

[0054] Figure 3 : is a diagram of the improved electrode plate arrangement structure of the present invention, wherein a and b are battery cells, and c is a battery stack;

[0055] Figure 4 : is the charge and discharge curve of Example 4 of the present invention;

[0056] Figure 5 is the charge and discharge curve of Example 5 of the present invention;

[0057] Figure 6 is the charge and discharge curve of Example 6 of the present invention;

[0058] 1. Isolate the guide plate. DETAILED DESCRIPTION

[0059] The present invention is further described in detail below in conjunction with the accompanying drawings:

[0060] The experimental methods used in the embodiments of the present invention are conventional methods unless otherwise specified.

[0061] The reagents and materials used in this example can all be purchased conventionally.

[0062] The electrode plates of the battery cell or battery stack in the present invention can be arranged in parallel, such as Figure 2 shown.

[0063] In order to facilitate the active material falling off the positive plate to sink to the negative plate under the action of gravity, the electrode plate in the battery cell can be arranged so that the bottom end of the negative plate extends below the positive plate (such as Figure 3 a) Or use the negative electrode as a container for electrolyte and immerse the positive electrode in the electrolyte in the container (e.g. Figure 3 b) or the negative plate extends toward the positive plate and the bottom end of the negative plate is connected to the bottom end of the positive plate through an isolation guide plate 1 (such as Figure 3 c) The side of the isolation guide plate 1 connected to the positive plate is higher than the side connected to the negative plate, so that the lead dioxide falling off the positive plate can sink to the negative plate under the action of gravity.

[0064] In Examples 1 to 5 and Comparative Example 1, the width of the single-sided conductive plastic plate (the other side is insulated with tape) is 1 cm.

[0065] Comparative Example 1

[0066] A quartz cup was filled with 40 mL of water-soluble lead-acid electrolyte containing 1.5 mol / L lead fluoroborate, 1 mol / L fluoroboric acid, and 0.01 mol / L ferrous methanesulfonate. The positive and negative electrodes were both single-sided conductive plastic plates, and the positive and negative electrodes were inserted parallel to the electrolyte to a depth of 1 cm (i.e., an effective area of ​​1 cm). 2 ), with a spacing of 2.5 cm, and the structure is as follows Figure 2 As shown in a, the battery was stirred at 300 rpm with a magnetic stirrer; the battery was charged and discharged at a constant current of 20 mA, with an upper voltage limit of 2.5 V and a lower voltage limit of 0 V. The charging time was 4 h, and the battery was cycled 3 times, taking 21.983 h. The average current efficiency was only 83.2%.

[0067] Continue to add ferrous methanesulfonate to 0.05 mol / L, keep stirring; 20 mA constant current charge and discharge, voltage upper limit 2.5 V, lower limit 0 V, 1 cycle, time 5.642 h, current efficiency is only 41.1%. It shows that with the increase of iron concentration, the current efficiency drops seriously.

[0068] Example 1

[0069] A quartz cup was filled with 40 mL of water-soluble lead-acid electrolyte containing 1.5 mol / L lead fluoroborate, 1 mol / L fluoroboric acid, and 0.01 mol / L ferrous methanesulfonate. The positive and negative electrodes were both single-sided conductive plastic plates, inserted into the electrolyte to a depth of 1 cm (i.e., an effective area of ​​1 cm). 2 ), with a spacing of 2.5 cm, and the structure is as follows Figure 2 As shown in a, the solution remained stationary; 20 mA constant current charging and discharging, the voltage upper limit was 2.5 V, the lower limit was 0 V, the charging time was 4 h, the cycle was repeated 5 times, the time was 38.733 h, and the average current efficiency was 93.7%.

[0070] Compared with Comparative Example 1, Example 1 has a higher current efficiency, indicating that keeping the solution still during the charge and discharge process can effectively prevent self-discharge caused by convective diffusion of the lead dissolving agent. After completing the charge and discharge, there is a small amount of solid lead dioxide at the bottom of the positive electrode. The lead and lead dioxide on the electrode are completely dissolved by stirring at 300 rpm with a magnetic stirrer for 8 h, and there is no solid lead residue at the bottom of the container, indicating that the water-soluble lead-acid static battery can maintain good stability.

[0071] Continue to add ferrous methanesulfonate to 0.05 mol / L, stir the electrolyte evenly and keep it still; 20 mA constant current charge and discharge, the voltage upper limit is 2.5 V, the lower limit is 0 V, the charging time is 4 h, the cycle is 5 times, the time is 36.455 h, and the current efficiency is 82.3%, which is lower than the current density when the iron content is 0.01 mol / L, indicating that the increase in the lead dissolving agent content will accelerate the self-discharge, but it is significantly higher than the comparative example 1, indicating that in the absence of a diaphragm and the flow of electrolyte, iron ions / ferrous ions shuttle back and forth between the positive and negative electrodes, resulting in serious self-discharge. Therefore, the traditional diaphragm-free water-soluble lead-acid flow battery is not suitable for electrolytes containing lead dissolving agents.

[0072] After charging and discharging, there is a small amount of lead dioxide at the bottom of the positive electrode. After stirring with a magnetic stirrer at 300 rpm for 10 min, the lead dioxide at the bottom of the container is completely dissolved. After stirring for another 8 h, most of the lead is dissolved, indicating that increasing the content of lead dissolving agent will accelerate the dissolution of lead dioxide, but has no significant effect on the oxygen absorption and dissolution of lead.

[0073] Example 2

[0074] A quartz cup was filled with 40 mL of water-soluble lead-acid electrolyte containing 1.5 mol / L lead fluoroborate, 1 mol / L fluoroboric acid, and 0.05 mol / L ferrous methanesulfonate. The positive electrode was a single-sided conductive plastic plate inserted into the electrolyte to a depth of 1 cm (i.e., an effective area of ​​1 cm). 2 ), the negative electrode is a nickel sheet, which is clamped by an L-shaped electrode clamp. The negative electrode is set in the horizontal direction and is located about 1 cm below the positive electrode. The structure is as follows Figure 3 As shown in a (the vertical direction here is the insulating part of the electrode clamp), the solution remained static; 20 mA constant current charging and discharging, the voltage upper limit was 2.5 V, the lower limit was 0 V, the charging time was 4 h, the cycle was repeated 5 times, the time was 35.701 h, and the current efficiency was 78.5%.

[0075] After the charge and discharge are completed, no lead dioxide remains on the surface of the negative electrode under the positive electrode, indicating that the lead dioxide precipitates on the surface of the negative electrode and is quickly dissolved; after leaving the container open for 24 hours, most of the lead on the surface of the negative electrode absorbs oxygen and dissolves, indicating that static batteries, especially the structure in which the negative electrode extends to under the positive electrode, can allow the electrolyte to be used for a long time under completely static conditions while maintaining stable composition.

[0076] Example 3

[0077] A quartz cup was filled with 40 mL of water-soluble lead-acid electrolyte containing 1.5 mol / L lead methanesulfonate, 1 mol / L methanesulfonic acid, 0.05 mol / L ferrous methanesulfonate, and 0.01 mol / L hexadecyltrimethylammonium methylsulfate. The positive electrode was a single-sided conductive plastic plate inserted into the electrolyte to a depth of 1 cm (i.e., an effective area of ​​1 cm). 2 ), the negative electrode is a nickel sheet, which is clamped by an L-shaped electrode clamp. The negative electrode is set in the horizontal direction and is located about 1 cm below the positive electrode. The structure is as follows Figure 3 As shown in a (the vertical direction here is the insulating part of the electrode clip), the solution remained static; 20 mA constant current charge and discharge, the voltage upper limit was 2.5 V, the lower limit was 0 V, the charging time was 4 h, the cycle was repeated 5 times, the time was 35.412 h, the current efficiency was 77.1%, and no obvious dendrite growth or shedding was observed at the edge of the electrode (high current density area).

[0078] Example 4

[0079] A nickel container was filled with 15 mL of water-soluble lead-acid electrolyte containing 1.5 mol / L lead fluoroborate, 1 mol / L fluoroboric acid, and 0.02 mol / L ferrous fluoroborate. The positive electrode was a single-sided conductive plastic plate inserted into the electrolyte to a depth of 1 cm (i.e., an effective area of ​​1 cm). 2 ), the structure is as follows Figure 3 As shown in b, the solution remained stationary; 20 mA constant current charging and discharging, the voltage upper limit was 2.5 V, the lower limit was 0 V, the charging time was 4 h, the cycle was repeated 5 times, the time was 37.844 h, the current efficiency was 89.2%, and the charge and discharge curves were shown in Figure 4 .

[0080] During the test, there was no solid lead dioxide at the bottom of the container, and the charge and discharge voltage began to stabilize from the 5th cycle; the container was in an open state and there was almost no lead residue.

[0081] Example 5

[0082] A nickel container was filled with 15 mL of water-soluble lead-acid electrolyte containing 1.5 mol / L lead fluoroborate, 1 mol / L fluoroboric acid, and 0.01 mol / L VO(BF4)2. The positive electrode was a single-sided conductive plastic plate inserted into the electrolyte to a depth of 1 cm (i.e., an effective area of ​​1 cm). 2 ), the structure is as follows Figure 3 As shown in b, the solution remained stationary; 20 mA constant current charging and discharging, the voltage upper limit was 2.5 V, the lower limit was 1 V, the charging time was 2 h, the cycle was repeated 5 times, the current efficiency was 91.6%, and the charge and discharge curves were shown in Figure 5 .

[0083] During the test, there was no lead dioxide solid at the bottom of the container.

[0084] Example 6

[0085] The plastic box was divided into compartments by three 5 cm × 10 cm conductive plastic bipolar plates (electrolytes in different compartments could not flow into each other). The conductive plastic bipolar plates were placed in parallel with a distance of 2 cm between adjacent conductive plastic plates to obtain a static battery stack with two cells connected in series. 50 ml of electrolyte was poured into each cell compartment. The electrolyte contained 1.5 mol / L lead fluoroborate, 1 mol / L fluoroboric acid, and 0.01 mol / L ferrous fluoroborate. The effective area of ​​each cell bipolar plate was about 14 cm. 2 , the electrolyte in the compartment remains static, the electrodes at both ends and the middle bipolar plate are arranged in parallel; 200 mA constant current charging for 3.1 h, the voltage upper limit is 5 V, and then discharged to 2 V, 1 cycle takes 5.817 h, and the current efficiency is 87.6%. The test results are shown in Figure 6 .

[0086] In terms of battery structure, traditional flow battery stacks usually adopt a single-cell series assembly method. This method is simple and convenient, can make full use of the bipolar plate, and does not require high conductivity of the bipolar plate. However, the electrolyte is connected between the cells of the traditional series-connected battery stack. The inventors found that the conventional battery stack design has serious technical defects for water-soluble lead-acid flow batteries. In order to explain this problem more clearly, Figure 1The structure of the traditional series-type battery stack (two cells in series) is given, including the battery stack with and without a diaphragm. When charging, most of the current starts from the left end plate, passes through the middle bipolar plate, and reaches the right end plate (i.e., effective current I1), and a considerable part of the current starts from the left end plate and flows along the electrolyte pipeline to the right end plate (i.e., I2), causing a short circuit; after charging stops, there is a potential difference between the active materials on both sides of the middle bipolar plate, and the electrolytes on both sides are connected through the pipeline, forming a closed loop (I3), causing self-discharge. For all-liquid flow batteries, such as all-vanadium flow batteries and iron-chromium flow batteries, since there is no active material deposition involved and very little active material is stored in the battery stack, the impact of current I2 and I3 is limited (usually only reduces current efficiency and energy efficiency), and therefore difficult to detect. However, for water-soluble lead-acid flow batteries, the positive and negative active materials are all deposited on the bipolar plates. Short circuits during charging will cause differences in the surface capacity of different bipolar plates. After charging stops, all bipolar plates except the left and right end plates have serious self-discharge, resulting in serious surface capacity reduction and energy loss. For this problem, although each battery cell can be equipped with an independent liquid flow pump to solve it, it will greatly increase the volume and complexity of the battery stack, and greatly increase the cost. In addition, facilities such as electrolyte pipelines and liquid storage tanks have greatly increased the complexity of the energy storage system, reducing the energy density of the flow battery, increasing costs, and losing portability. Therefore, the electrolytes of different battery cells in the present application are isolated from each other, thereby avoiding short circuit caused by partial current moving along the electrolyte between the plates during charging and self-discharge caused by the potential difference of active materials between the electrolytes connected on both sides of the bipolar plates after charging is stopped.

[0087] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all details in detail, nor do they limit the invention to only the specific implementation methods described. Obviously, many modifications and optimizations can be made based on the content of this specification. These embodiments selected and specifically described in this specification are to better explain the principles and practical applications of the present invention, so that those skilled in the art can better understand and apply the present invention. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A water-soluble lead-acid static battery, characterized in that: The battery cell comprises an electrode plate, an electrolyte in a static state and a container for holding the electrolyte, the electrode plate is inserted in the electrolyte, the electrolyte composition comprises a water-soluble lead salt, an acid, a lead dissolving agent and water, the lead dissolving agent can provide at least one pair of water-soluble redox couple R 氧化 With R 还原 , the electrode potential of the redox couple satisfies E θ (Pb 2+ / Pb)< E θ (R 氧化 / R 还原 ) <E θ (PbO2 / Pb 2+ ).

2. The water-soluble lead-acid static battery according to claim 1, characterized in that: The battery is a battery stack composed of a group of battery cells or at least two groups of battery cells connected in series; when the battery is a battery stack composed of battery cells connected in series, the electrolytes between different battery cells are isolated.

3. The water-soluble lead-acid static battery according to claim 2, characterized in that: When the battery is a battery stack composed of battery cells connected in series, the electrode plates on both sides are used as the positive electrode and the negative electrode respectively, and the electrode plate between the positive electrode and the negative electrode is a bipolar plate, which is used to isolate the electrolyte phases between different battery cells.

4. The water-soluble lead-acid static battery according to claim 2, characterized in that: In a battery cell, the electrode plates include a positive plate and a negative plate, the bottom end of the negative plate extends below the positive plate and / or the bottom end of the negative plate is connected to the bottom end of the positive plate through an isolation guide plate; the isolation guide plate is used to guide the active material detached from the positive plate to the negative plate of the same battery cell under the action of gravity.

5. The water-soluble lead-acid static battery according to claim 4, characterized in that: The negative electrode is used as a container for the electrolyte, and the positive electrode is immersed in the electrolyte in the container.

6. The water-soluble lead-acid static battery according to claim 1, characterized in that: The electrolyte is in communication with the air.

7. The water-soluble lead-acid static battery according to claim 1, characterized in that: The lead dissolving agent includes one or more of water-soluble iron salts, ferrous salts, vanadium (V) salts, vanadium (IV) salts, and vanadium (III) salts.

8. The water-soluble lead-acid static battery according to claim 1, characterized in that: The lead dissolving agent is one or more of methane sulfonate and fluoroborate; the water-soluble lead salt is one or more of lead methane sulfonate and lead fluoroborate; and the acid is one or more of methane sulfonic acid and fluoroboric acid.

9. The water-soluble lead-acid static battery according to claim 1, characterized in that: The electrolyte shown includes the following components in concentrations: in mol / L, lead ions 0.05-3, hydrogen ions 0.001-8, iron ions 0-0.2, vanadium ions 0-0.2, methanesulfonate ions 0-8, and fluoroborate ions 0-8, wherein the concentrations of the methanesulfonate and fluoroborate ions are not simultaneously 0, and the concentrations of the iron and vanadium elements are not simultaneously 0.

10. The water-soluble lead-acid static battery according to claim 1, characterized in that: It also includes a lead dendrite inhibitor, which is one or more of methyl sulfate, methyl sulfonate, and fluoroborate of alkyl trimethylammonium, and the alkyl group is a straight chain with 12-22 carbon atoms.

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