Water-soluble lead-acid static battery

Abstract

The invention belongs to the technical field of electrochemical energy storage, and particularly relates to a water-soluble lead-acid static battery. 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 electrode potential of the redox couple meets E theta (Pb < 2 + > / Pb) lt; e [theta] (R oxidation / R reduction) [lt]; e theta (PbO2 / Pb2 +); the electrodes comprise a positive electrode and a negative electrode, the included angle between the positive electrode and the horizontal plane and the included angle between the negative electrode and the horizontal plane do not exceed 15 degrees, the positive electrode is arranged above the negative electrode, the horizontal projection of the positive electrode falls into the horizontal projection of the negative electrode, and the negative electrode is arranged at the bottom of the container. According to the method, the density difference caused by the solution concentration difference and the lead ion sinking effect caused by the density difference can be fully utilized, the problems of slow static battery solute diffusion, non-uniform solid lead deposition-dissolution and bottom lead dendritic crystal growth are solved, and the battery capacity and the energy efficiency are improved.

Description

Technical Field

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

[0002] A water-soluble lead-acid static battery is a secondary battery in which electrodes are disposed in an electrolyte (an aqueous solution of a water-soluble lead salt, an acid, and a lead solvent), and the electrolyte remains static during charge and discharge. During charging, lead ions in the electrolyte are converted into conductive solid lead (lead at the negative electrode and lead dioxide at the positive electrode) and deposited on the surface of the electrodes; during discharging, the solid lead dissolves into lead ions and enters the electrolyte; the lead dioxide powder shed from the positive electrode can reach the surface of the negative electrode through gravity sedimentation and dissolve during discharging under the promotion of the lead solvent. Keeping the electrolyte static can avoid self-discharge caused by the shuttle of the lead solvent between the positive and negative electrodes, and greatly simplify the battery structure, reduce the production and maintenance costs, and improve the reliability.

[0003] However, there are still some problems with water-soluble lead-acid static batteries, which are directly manifested as: (1) the capacity of a single battery cell is limited; (2) the deposition of lead on the surface of the electrodes is uneven, and lead dendrite growth even occurs at the negative electrode of some batteries (especially the battery structure connected in series into a battery stack); (3) the energy efficiency is not high.

[0004] The above problems are mainly caused by the following factors: (i) Slow diffusion of lead ions. Since the static battery eliminates the circulation pump and the liquid storage tank, lead ions diffuse only relying on the concentration gradient. When the distance between the positive and negative electrodes is shortened, the internal resistance of the battery decreases, but the electrolyte in the electrode gap also decreases accordingly. Although increasing the electrode distance or adding electrolyte in the area outside the electrode gap can increase the capacity, these methods will increase the diffusion distance of lead ions, thereby increasing the internal resistance of the battery. (ii) The density difference of the solution caused by the solute concentration difference. Since the density of the electrolyte is positively correlated with the concentration of lead ions, during the charging process, the concentration of lead ions in the solution on the electrode surface decreases, resulting in the local solution density being lower than that of the surrounding area. And because the diffusion of lead ions is slow, the concentration difference cannot be eliminated. The low-density solution floats to the liquid surface under the action of gravity and liquid pressure, and vice versa during the discharging process. The charging and discharging processes ultimately lead to the accumulation of lead ions at the bottom of the container. In addition, in the area with low lead ion concentration, solid lead is difficult to form and easy to dissolve, while in the area with high lead ion concentration, it is the opposite; therefore, the lead ion concentration decreases from bottom to top, resulting in uneven distribution of solid lead on the electrode (decreasing from bottom to top), and further exacerbating the accumulation of lead ions at the bottom of the container; in particular, a large amount of lead deposition at the bottom of the negative electrode will promote the growth of lead dendrites, thereby causing a short circuit. (iii) The difference in electrode potential in the vertical direction. According to the Nernst equation, the concentration difference of the electrolyte will cause a difference in electrode potential. Therefore, there is a potential difference in the vertically arranged electrodes. This potential difference increases the energy loss during the charging and discharging processes, thereby reducing the energy efficiency. Under the combined action of the above factors, the capacity and energy efficiency of the existing water-soluble lead-acid static battery are severely limited. Summary of the Invention

[0005] In view of the above problems existing in the prior art, the present invention provides a water-soluble lead-acid static battery, which can make full use of the density difference caused by the solution concentration difference and the resulting lead ion sinking effect, solve problems such as slow solute diffusion, uneven solid lead deposition, and growth of lead dendrites at the bottom in the static battery, and improve the battery capacity and energy efficiency.

[0006] To achieve the above object, the technical solution provided by the present invention is as follows:

[0007] The present application provides a water-soluble lead-acid static battery, including a battery cell. The battery cell includes electrodes, a static electrolyte, and a container for holding the electrolyte. The electrodes are arranged in the electrolyte. The electrolyte composition includes a water-soluble lead salt, an acid, a lead solvent, and water. The lead solvent can provide at least one pair of water-soluble redox couples R 氧化 and R 还原 , and 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+ );The electrode includes a positive electrode and a negative electrode. The included angle between the positive electrode and the negative electrode and the horizontal plane does not exceed 15°. The positive electrode is above the negative electrode and the horizontal projection of the positive electrode falls within the horizontal projection of the negative electrode. The negative electrode is arranged at the bottom of the container.

[0008] Optionally, the negative electrode is arranged to fit the inner side of the bottom wall of the container.

[0009] Optionally, the negative electrode is used as the bottom wall of the container or the container for containing the electrolyte.

[0010] Optionally, the arrangement height of the positive electrode in the electrolyte is 0.1 - 0.5 times the height of the electrolyte.

[0011] Optionally, both the positive electrode and the negative electrode are horizontally arranged.

[0012] Optionally, the horizontal projection area of the positive electrode is smaller than that of the negative electrode.

[0013] Optionally, a battery cell includes one or more positive electrodes and one or more negative electrodes; multiple positive electrodes in the same battery cell are connected in parallel, and multiple negative electrodes are connected in parallel.

[0014] Optionally, the battery includes a stack composed of at least two groups of battery cells connected in series; the electrodes at the top and bottom are used as the positive electrode and the negative electrode respectively, the electrodes between the positive electrode and the negative electrode use bipolar plates, the electrolytes between the battery cells on the upper and lower sides of the bipolar plate are isolated, the upper surface of the bipolar plate is the negative electrode, and the lower surface is the positive electrode.

[0015] Optionally, the water-soluble redox couple includes one or more of Fe 3+ / Fe 2+ , VO2 + / VO 2+ , VO 2+ / V 3+ and the like.

[0016] Optionally, the lead solvent includes one or more of methyl sulfonate and fluoroborate; the water-soluble lead salt includes one or more of lead methyl sulfonate and lead fluoroborate; the acid includes one or more of methyl sulfonic acid and fluoroboric acid.

[0017] Optionally, the electrolyte includes the following components in the following concentrations: in mol / L, lead ion 0.05 - 3, hydrogen ion 0.001 - 8, iron element 0 - 0.2, vanadium element 0 - 0.2, methyl sulfonate ion 0 - 8, fluoroborate ion 0 - 8. The concentrations of the methyl sulfonate ion and the fluoroborate ion are not both 0 at the same time, and the concentrations of the iron element and the vanadium element are not both 0 at the same time.

[0018] Optionally, the electrode or the bipolar plate is one or more of conductive plastics, graphite, graphite felt, copper, nickel, and stainless steel.

[0019] Compared with the prior art, the present application has at least the following beneficial effects:

[0020] The present invention makes full use of the density difference caused by the concentration difference of the electrolyte solute. During the charging process driven by gravity and concentration difference, lead ions outside the electrode gap can quickly gather into the electrode gap, and flow out from the electrode gap and spread flat on the bottom of the container during the discharging process, increasing the diffusion area, thereby realizing the efficient mass transfer of the electrolyte under static conditions.

[0021] The local lead ion concentration on the surface of the negative electrode can be maintained at the highest level in the whole solution, effectively inhibiting the growth of lead dendrites towards the positive electrode; the lead ion concentration on the surface of the positive electrode is relatively high and evenly distributed, effectively reducing the electrode concentration polarization and improving the energy efficiency.

[0022] The battery monomer has a high capacity and can store energy for a long time of more than 8 hours; the battery monomers can be stacked in layers in series to form a battery stack, with high flexibility, which can save the top cover material and is easy to assemble, repair and recycle. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 is the schematic diagram of the working principle of the water-soluble lead-acid static battery of the present application;

[0024] Figure 2 is the structural diagram of the water-soluble lead-acid static battery of the present application;

[0025] Figure 3 is the test result of the comparative example of the present application; where a corresponds to Comparative Example 1, b corresponds to Comparative Example 2, and c corresponds to Comparative Example 3;

[0026] Figure 4 is the charge and discharge test curve (a) of Example 1 of the present application and the electrode after the test (b);

[0027] Figure 5 is the charge and discharge test curve (a) of Example 2 of the present application and the electrode after the test of Example 2 and Comparative Example 3 (b);

[0028] Figure 6 is the charge and discharge test curve of Example 3 of the present application. DETAILED DESCRIPTION OF THE INVENTION

[0029] The following further describes the present invention in detail with reference to the drawings:

[0030] The experimental methods used in the embodiments of the present invention are all conventional methods unless otherwise specified.

[0031] The reagent materials used in this example can be purchased routinely.

[0032] The composition of the aqueous lead-acid static battery electrolyte in the embodiments of this application is as follows:

[0033] In Comparative Examples 1-2, Example 1 and Example 3: lead borofluoride 1.5 mol / L, boric acid fluoride 1 mol / L, vanadyl(IV) borofluoride 0.01 mol / L;

[0034] In Comparative Example 3 and Example 2: lead borofluoride 1.5 mol / L, boric acid fluoride 1 mol / L, ferrous borofluoride 0.01 mol / L.

[0035] The schematic diagram of the principle of action of the aqueous lead-acid static battery of this application is as Figure 1 , and the structure of the battery is as Figure 2 shown, and any one of Figure 2 a-f can be adopted. As Figure 1 shown, the electrodes are horizontally arranged at the bottom of the container. During the charging process, the electrolyte in the electrode gap has a lower density than the surrounding due to the consumption of lead ions, so it floats to the liquid surface. At the same time, the solution with a high concentration of lead ions around quickly flows into the electrode gap; during the discharging process, the electrolyte in the electrode gap has a higher density than the surrounding due to the increase in the concentration of lead ions. The high-density solution flows to the surrounding and spreads flat at the bottom of the container, increasing the area for exchanging solutes (i.e., diffusion) with the upper solution; a small amount of lead dioxide shed from the positive electrode can settle on the surface of the negative electrode and discharge and dissolve under the action of the lead solvent.

[0036] Specifically, the growth of negative lead dendrites occurs during the charging process, and its growth process is mainly affected by lead ion concentration and current. First, since the essence of lead deposition is that lead ions in the solution gain electrons when colliding with the nearby negative electrode and deposit on the electrode surface. In this process, the higher the lead ion concentration, the more conducive it is to deposition. Second, the conductivity of the electrode is usually higher than that of the solution. If the solution concentration is uniform, the shortest route between the two electrodes is usually the path with the smallest resistance, which is also the fastest path for the growth of lead dendrites. If there are protrusions on the electrode surface, the current density at the protrusions is large, further exacerbating the growth of lead dendrites. In addition, due to the consumption of lead ions on the negative electrode surface, lead dendrites tend to grow towards the region with high concentration, that is, the region far from the electrode surface, which further exacerbates the growth of lead dendrites. Therefore, lead dendrites usually grow in the direction of high lead ion concentration and reverse current. However, in the setting of this application, the lead ion concentration decreases upward from the negative electrode surface, and the lead ion concentration on the negative electrode surface is the highest. According to the influence of concentration, lead tends to deposit smoothly on the negative electrode surface because moving away from the negative electrode is the direction in which the lead ion concentration decreases, which is not conducive to lead deposition. According to the influence of current, lead dendrites have a tendency to grow upward. However, due to the horizontal setting of the positive electrode, compared with the vertical setting, its horizontal projection area increases significantly, effectively reducing the local current density (the region where the horizontal projections of the positive and negative electrodes overlap), thereby delaying the growth of lead dendrites. Considering the above two factors comprehensively, the growth of lead dendrites is significantly inhibited.

[0037] The electrodes horizontally arranged at the bottom of the container in this application make full use of the density difference to quickly replenish the lead ions outside the electrode gap to the electrode surface, and its efficiency is much higher than the diffusion driven by the concentration gradient, realizing the efficient expansion of the static battery monomer; the horizontally arranged electrodes reduce the concentration difference at each part of the electrode, thereby reducing the electrode polarization caused by the concentration difference and improving the energy efficiency. In addition, since the appropriate inclination of the positive electrode is beneficial to the discharge of oxygen bubbles generated by oxygen evolution, the included angle between the electrode and the horizontal plane can be within 15°.

[0038] Comparative Example 1

[0039] Take a 1 cm × 25 cm copper strip as the negative electrode and a 1 cm × 20 cm conductive plastic plate as the positive electrode. One side of the plastic plate is pasted with a copper strip as the current collector using conductive glue and sealed with insulating tape, and the other side is used as the electrode surface; keep the positive and negative electrodes parallel and vertical, place them in a 100 mL glass graduated cylinder until they touch the bottom of the cylinder, and pour 100 mL of electrolyte with a liquid level height of 17 cm, thus forming an existing water-soluble lead-acid static battery.

[0040] The charging current is 0.6 A, the upper limit of the charging voltage is 2.5 V, and the duration is 4 h; the lower limit of the discharge voltage is 0.5 V. First, discharge at a current of 0.6 A, and continue to discharge at a current of 0.1 A until the voltage drops to the lower limit after the voltage drops to the lower limit.

[0041] During the charging process, it was observed that the refractive index of the solution on the electrode surface was significantly different from that of the surrounding solution, and there was a floating phenomenon. This was due to the rapid consumption of lead ions on the electrode surface, which caused the refractive index of the local solution to change. At the same time, due to the decrease in density, it appeared to float. Similarly, during the discharge process, the lead ion concentration on the electrode surface increased, the density increased, and it appeared to sink. After the charging was completed, lead dendrites appeared at the edge of the negative electrode. After the discharge was completed, due to the large amount of positive electrode active material falling off, the first cycle current efficiency was only 70.4%.

[0042] The charge and discharge were repeated again. After the charge was completed, the thickness of the lead deposits on the negative electrode decreased from the bottom to the top. After the discharge was completed, the electrode was taken out and the electrolyte in the measuring cylinder was stirred. It was found that there was a difference in the refractive index of the upper and lower layers of the measuring cylinder, indicating that there was a significant concentration difference in the electrolyte solute in the vertical direction. Figure 3 a. Figure 3 a shows that the deposition and dissolution of lead in the vertical direction is not uniform. It can be clearly observed at the negative electrode that the lead near the liquid surface is completely dissolved, exposing the copper electrode base. The boundary between the copper base and the lead appears 13.5 cm from the bottom, while at 1.2 cm from the bottom, due to the large accumulation of single lead, lead dendrites grow in the horizontal direction.

[0043] This comparative example shows that in a water-soluble lead-acid static battery with vertically arranged electrodes, the deposition and dissolution of lead in the vertical direction is uneven, and lead ions and solid lead tend to gather at the bottom of the container. In particular, a large amount of lead accumulates at the bottom of the negative electrode, which aggravates the growth of lead dendrites and severely limits the increase in battery capacity.

[0044] Comparative Example 2

[0045] Take 15 mL of electrolyte and place it in a nickel container with a volume of 20 mL; extend a conductive plastic plate with a width of 1 cm into the electrolyte to a depth of 1 cm and an effective area of ​​2 cm 2 , the bottom end of the conductive plastic plate is 1 cm away from the bottom of the container; it is sealed with a sealing film, the nickel container is used as the negative electrode, and the conductive plastic plate is used as the positive electrode, thus constituting an existing water-soluble lead-acid static battery.

[0046] The charge and discharge current is 40 mA, the maximum duration is 8 h, the voltage upper limit is 2.5 V, the lower limit is 0 V, and the cycle is 7. The test results are shown in Figure 3 b, The average current efficiency of 7 cycles is 89.7%, the average charging voltage is 2.164 V, the discharge voltage is 1.385 V, and the energy efficiency is 57.4%.

[0047] Since the bottom of the nickel container is horizontal, lead can be evenly deposited on the bottom of the container, but little lead is deposited on the vertical walls, indicating that the utilization rate of the vertical part of the negative electrode is not high, while the lead deposition efficiency on the horizontal part of the container bottom is high. The positive electrode is similar to Comparative Example 1, and there is a small amount of lead dioxide residue at the bottom end of the conductive plastic plate. This comparative example shows that in order to improve the electrode utilization efficiency, both the positive and negative electrodes should be horizontally arranged.

[0048] Comparative Example 3

[0049] Take a plastic square box with an internal bottom size of 10 cm × 10 cm and a height of 5 cm. Cover the bottom of the plastic box with a long strip of copper tape with a width of 10 cm, and bend the excess part of the copper tape upward along the box as a lead wire to lead out; Pour 200 mL of electrolyte into the above container, keep the 4 cm × 10 cm conductive plastic plate with the long side vertically downward, and vertically insert it into the electrolyte to a depth of 1.5 cm, that is, the effective area is 30 cm 2 , and the bottom end of the conductive plastic plate is 0.5 cm away from the bottom of the container; Use the conductive plastic plate as the positive electrode and the copper tape as the negative electrode, that is, a kind of existing water-soluble lead-acid static battery is formed.

[0050] The charge and discharge currents are both 450 mA, the maximum duration is both 12 h, the upper voltage limit is 2.5 V, the lower limit is 0 V, and it is cycled 3 times. The test results are shown in Figure 3 c. The average current efficiency for 3 cycles is 83.9%, the average charging voltage is 2.202 V, the average discharging voltage is 1.393 V, and the energy efficiency is 53.1%.

[0051] After 3 cycles, there is metallic lead residue on the negative copper tape, and there are no obvious dendrites; However, it can be seen from Figure 3 c that during the charging process, there is a phenomenon of sudden drop in the charging voltage, presumably due to the growth of a small amount of dendrites leading to a short circuit, and the short circuit intensifies with the increase in the number of cycles; The positive electrode is similar to Comparative Examples 1-2, and there is a small amount of lead dioxide residue at the bottom end. After short-circuiting and discharging overnight by connecting the positive and negative electrodes with a wire, it still cannot be dissolved, as shown in Figure 5 b. This comparative example shows that in the existing water-soluble lead-acid static battery, the positive electrode is vertically arranged. As the distance from the positive electrode approaches and the charge and discharge capacity increases, the short-circuit phenomenon caused by the growth of lead dendrites intensifies, seriously limiting the improvement of the battery capacity.

[0052] Example 1

[0053] Place 50 mL of electrolyte in a quartz jar with a volume of 100 mL; Clamp a 2.5 cm × 2.5 cm copper sheet with an L-shaped electrode clamp, and insert the copper sheet into the electrolyte so that it is close to the bottom of the container and placed horizontally; Seal one side of a 2 cm × 2 cm conductive plastic plate with insulating tape and clamp it with an L-shaped electrode clamp. After clamping, the effective area on the conductive side is 3.75 cm2 , keep the conductive side of the conductive plastic plate horizontal and facing downward, so that it is located 1 cm above the copper sheet; cover the mouth of the jar with a lid, with the copper sheet as the negative electrode and the conductive plastic plate as the positive electrode, forming Figure 2 The water-soluble lead-acid static battery shown in a utilizes density difference.

[0054] The charge and discharge current is 80 mA, the maximum duration is 15 h, the upper voltage limit is 2.5 V, the lower voltage limit is 0 V, and the cycle is 5 cycles. Figure 4 a. During the test, no lead dendrites were observed on the negative electrode. After the test, the electrode showed Figure 4 b. The average current efficiency of 5 cycles is 86.2%, the average charging voltage is 2.053 V, the average discharging voltage is 1.532 V, and the energy efficiency is 64.3%, which is significantly higher than that of Comparative Example 2.

[0055] The positive electrode surface capacity of this embodiment exceeds 300 mAh / cm 2 , and there is no lead dendrite on the negative electrode in the fully charged state, and there is still room for further charging, indicating that the water-soluble lead-acid static battery provided by the present invention has an extremely high surface capacity. Figure 4 In b, a small amount of copper substrate is exposed, and the exposed part is the part of the copper sheet that is warped upward (the height of the warp at the edge is less than 1 mm). The edge is closer to the positive electrode and is sharp, which is conducive to the growth of lead dendrites. However, due to the sinking of lead ions, the residual lead is not deposited in this part, but deposited in the low-lying area, resulting in a "peak shaving and valley filling" phenomenon. This shows that in water-soluble lead-acid static batteries, the lead dendrite growth-dissolution process is dominated by concentration.

[0056] Example 2

[0057] The plastic box and copper tape negative electrode used in Comparative Example 3 were used, and 200 mL of electrolyte was poured in. A 2 cm × 9.5 cm conductive plastic plate and a 1 cm wide titanium tape were taken, and one side of the conductive plastic plate was coated with conductive glue, and a titanium tape was attached as a current collector, and then an insulating tape was attached. The other side was the electrode surface, with an effective area of ​​18 cm 2 Place the electrode surface downward in the above-mentioned plastic box containing electrolyte, with a depth of 1.5 cm and a distance of 0.5 cm from the negative electrode, as the positive electrode of the battery. Figure 2 The water-soluble lead-acid static battery shown in a utilizes density difference.

[0058] The charge and discharge current is 270 mA, the maximum duration is 12 h, the upper voltage limit is 2.5 V, the lower voltage limit is 0 V, and the cycle is 4. The charge and discharge test data is shown in Figure 5 a. No lead dendrite growth was observed during the test. The electrode after the test was completed Figure 5 b. From Figure 5It can be seen that the voltage in this embodiment is very stable, the current efficiency is high, the average current efficiency for 4 cycles is 93.2%, the average charging voltage is 2.119 V, the average discharging voltage is 1.497 V, and the energy efficiency is 65.8%.

[0059] Compared with Comparative Example 3, the voltage efficiency in this embodiment is higher because the positive electrode layout in this embodiment eliminates the concentration difference on the surface of the positive electrode, reduces the electrode polarization; at the same time, the reduction of the concentration difference also promotes the full discharge and dissolution of the active substances on the surface of the positive electrode. After the test, the residual lead dioxide on the positive electrode surface is less and evenly distributed, so the current efficiency is high; while for the positive electrode of Comparative Example 3, the lead dioxide at the bottom cannot be fully dissolved and the residue is large, resulting in low current efficiency. The energy efficiency of this embodiment is 23.9% higher than that of Comparative Example 3, and the stability is greatly improved, which fully shows that the water-soluble lead-acid static battery of the present invention improves the energy efficiency. In addition, the residual lead at the negative electrode of this embodiment is also filled in the low-lying areas of the negative electrode.

[0060] Example 3

[0061] Fabrication Figure 2 For the bowl-shaped container in the stack shown in e, the inner diameter of the vertical part of the container wall is 14 cm, the height is 2 cm, the included angle between the connecting part of the container wall and the horizontal plane is 45°, and the connecting part also serves as a guiding plate for collecting lead dioxide and guiding it to the negative electrode. The bottom of the container is a circular copper sheet with a diameter of 10 cm. A copper strip is pasted on the lower surface of the bottom of the container with conductive glue as the negative electrode lead. Take 260 mL of electrolyte and place it in the container; fabricate the above container with a conductive plastic plate at the bottom, and paste a copper mesh on the upper surface of the bottom of the container with conductive glue as the positive electrode lead. Stack this container on the container containing the electrolyte above to form a stack.

[0062] The charging current is 1.5 A, the upper limit of the charging voltage is 2.5 V, and the duration is 4 h; the lower limit of the discharging voltage is 0.5 V. First, discharge at a current of 1.5 A. After the voltage drops to the lower limit, continue to discharge at a current of 0.6 A until the voltage reaches the lower limit. The test results are shown in Figure 6 , and the current efficiency of the first cycle is 84.4%. Charge and discharge again. After the test, the lead deposition on the negative electrode surface is uniform, and no lead dendrite growth is observed.

[0063] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all details in detail, nor limit the invention to the specific embodiments described. Obviously, many modifications and optimizations can be made according to the content of this specification. These embodiments selected and specifically described in this specification are for better explaining the principle and practical application of the present invention, so that those skilled in the art can better understand and apply the present invention. The present invention is only limited by the claims and their full scope and equivalents.

Claims

1. A water-soluble lead-acid static battery, characterized in that, Comprising a battery cell, the battery cell including electrodes, an electrolyte in a static state, and a container for containing the electrolyte, the electrodes being disposed in the electrolyte, the electrolyte composition including a water-soluble lead salt, an acid, a lead solvent, and water, the lead solvent being capable of providing at least one pair of water-soluble redox couples R 氧化 and R 还原 , the electrode potential of the redox couple satisfying E θ (Pb 2+ / Pb) < E θ (R 氧化 / R 还原 ) < E θ (PbO2 / Pb 2+ ); the electrodes include a positive electrode and a negative electrode, the included angle between the positive electrode and the negative electrode with respect to the horizontal plane not exceeding 15°, the positive electrode being above the negative electrode and the horizontal projection of the positive electrode falling within the horizontal projection of the negative electrode, the negative electrode being disposed at the bottom of the container.

2. The water-soluble lead-acid static battery according to claim 1, wherein The negative electrode is arranged close to the inner side of the bottom wall of the container.

3. A water-soluble lead-acid static battery according to claim 1, characterized in that, The negative electrode serves as the bottom wall of the container or the container for holding the electrolyte.

4. A water-soluble lead-acid static battery according to claim 1, wherein The arrangement height of the positive electrode in the electrolyte is 0.1 - 0.5 times the height of the electrolyte.

5. A water-soluble lead-acid static battery according to claim 1, characterized in that Both the positive electrode and the negative electrode are horizontally arranged.

6. A water-soluble lead-acid static battery according to claim 1, characterized in that, The horizontal projection area of the positive electrode is smaller than that of the negative electrode.

7. A water-soluble lead-acid static battery according to claim 1, wherein A battery cell includes one or more positive electrodes and one or more negative electrodes; multiple positive electrodes of the same battery cell are connected in parallel, and multiple negative electrodes are connected in parallel.

8. A water-soluble lead-acid static battery according to claim 1, characterized in that, The battery includes a stack composed of at least two groups of battery cells connected in series; the electrodes at the top and bottom are used as the positive electrode and the negative electrode respectively, the electrodes between the positive electrode and the negative electrode adopt bipolar plates, the electrolytes between the battery cells on the upper and lower sides of the bipolar plates are isolated, the upper surface of the bipolar plate is the negative electrode, and the lower surface is the positive electrode.

9. A water-soluble lead-acid static battery according to claim 1, characterized in that, The water-soluble redox couple includes Fe 3+ / Fe 2+ , VO2 + / VO 2+ , VO 2+ / V 3+ or one or more of them.

10. A water-soluble lead-acid static battery according to claim 1, characterized in that, The lead solvent includes one or more of methyl sulfonate and fluoborate; the water-soluble lead salt includes one or more of lead methyl sulfonate and lead fluoborate; the acid includes one or more of methyl sulfonic acid and fluoboric acid.

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