A type of energy storage battery

Abstract

A new type of energy storage battery employs a structure with opposite terminals and a busbar. This design fully addresses the issues of acid stratification and uneven utilization of active materials between the upper and lower sections caused by excessively high plate height, leading to reduced battery life. This results in a more uniform current distribution and significantly improved charge acceptance and deep cycle life. The positive plate grid alloy undergoes pretreatment with pure lead combined with electroplating, avoiding the difficulties in forming a pure lead corrosion layer and insufficient adhesion to lead paste, thus improving battery conductivity and deep cycle life. Pore-forming agents and conductive agents are introduced into the positive electrode formulation to balance capacity and lifespan. The negative electrode formulation uses dendritic lead sulfate, significantly increasing the pore size and total pore volume after formation. During charging and discharging, this enhances ion transport channels, improves the utilization rate of negative active materials and fast charging capability, and delays battery sulfation. Simultaneously, the high-carbon formulation improves charge acceptance, and the dendritic lead sulfate prevents overcharging during negative electrode formation. Compared to traditional lead-acid energy storage batteries, this design extends battery life by at least 50%.

Description

Technical Field

[0001] This invention relates to the field of lead-acid battery technology, specifically a novel energy storage battery. Background Technology

[0002] With the national dual-carbon goals and the construction of a new energy structure, the demand for energy storage batteries is increasing. Currently, the mainstream electrochemical energy storage battery is the lithium-ion battery, mainly due to its longer lifespan and better energy conversion efficiency, but its lower safety is a significant concern in the industry. Lead-acid batteries are aqueous batteries and do not pose a risk of fire or explosion. However, as energy storage batteries, the biggest problem with lead-acid batteries is their short lifespan. Therefore, if lead-acid batteries want to gain a foothold in the energy storage market, they must focus on improving battery lifespan. The failure modes of lead-acid energy storage batteries include softening and shedding of the positive electrode active material, sulfation of the negative electrode, and corrosion of the positive electrode grid. Therefore, lifespan improvements should focus on these three aspects. In recent years, improvements to battery lifespan have mainly focused on materials, but structure and formulation are also major factors affecting lead-acid battery lifespan. Therefore, it is necessary to develop a new energy storage battery structure to improve the lifespan of lead-acid batteries and make them suitable for energy storage applications. Summary of the Invention

[0003] The purpose of this invention is to overcome the aforementioned shortcomings of the prior art and provide a novel energy storage battery suitable for energy storage applications. Combined with a unique positive and negative electrode formulation, it effectively extends the lifespan of energy storage lead-acid batteries. The specific technical solution is as follows:

[0004] The present invention provides an energy storage battery, comprising a battery case, a positive terminal, and a negative terminal; the battery case contains an electrolyte and an electrode group immersed in the electrolyte; the electrode group is composed of multiple positive electrode plates and multiple negative electrode plates arranged alternately with separators; the positive electrode plate includes a positive electrode grid and positive electrode paste coated on the positive electrode grid; the negative electrode plate includes a negative electrode grid and negative electrode paste coated on the negative electrode grid; a positive electrode bus and a negative electrode bus are provided on the electrode group; the positive electrode bus and the negative electrode bus respectively connect the tabs of all the positive and negative electrode plates of each electrode group, and the positive electrode bus and the negative electrode bus respectively connect to the positive terminal and the negative terminal.

[0005] The aspect ratio of the positive electrode plate is greater than or equal to 2; the aspect ratio of the negative electrode plate is greater than or equal to 2.

[0006] The positive and negative terminals are respectively disposed on opposite side walls of the battery compartment.

[0007] The positive electrode grid is made of pure lead alloy by continuous stamping process and is electroplated by the following steps: the positive electrode grid is immersed in electroplating solution, then cleaned and dried.

[0008] The electroplating solution is composed of the following raw materials in weight percentage: 0.19%~0.76% SnCl2, 0.72%~4.17% PbCl2, 0.77%~1.29% Na3C6H5O7 and 0.02~0.06% polyethylene glycol PEG-2000, with the balance being water.

[0009] The positive electrode lead paste is composed of the following raw materials by weight percentage: short fibers 0.06%~0.1%, pure water 10%~15%, 1.38g / cm³. 3 The solution contains 8%~11% sulfuric acid, 0.04%~0.1% antimony trioxide, 0.02%~0.08% tin dioxide, 0.05%~0.1% nano silica gel aqueous solution, 0.02%~0.04% expanded graphite, and the remainder is lead powder.

[0010] The negative electrode grid is made of PbCaSnAl alloy using a continuous stamping process.

[0011] The negative electrode lead paste is composed of the following raw materials by weight percentage: 12%~16% pure water, 0.1%~0.4% expanded graphite, and BET of 300~375 m. 2 / g carbon black 0.4~0.8%, barium sulfate 0.8~1.2%, lignin sulfonate 0.2~0.5%, short fiber 0.04%~0.08%, the remainder being dendritic lead sulfate.

[0012] The dendritic lead sulfate is prepared by vacuum filtration of soluble lead salt, (NH4)2SO4 and 0.01% polyethylene glycol PEG-2000 at room temperature; the molar ratio of soluble lead salt to (NH4)2SO4 is 0.8~1.

[0013] The electrolyte has a concentration of 1.26~1.30 g / cm³. 3 It is prepared by adding an electrolyte additive to a sulfuric acid solution; the electrolyte additive is one or both of potassium sulfate and lithium sulfate.

[0014] The positive terminal is located at the lower part of one side wall of the battery compartment, and the negative terminal is located at the upper part of the opposite side wall of the battery compartment.

[0015] There are multiple positive terminals and multiple negative terminals.

[0016] There are two positive terminals and two negative terminals.

[0017] There are two positive busbars: a lower positive busbar connected to the positive terminal and an upper positive busbar connected to the lower positive busbar; there are two negative busbars: an upper negative busbar connected to the negative terminal and a lower negative busbar connected to the upper negative busbar.

[0018] The positive electrode grid electroplating treatment is specifically as follows: the positive electrode grid is immersed in the electroplating solution and polarized with a potential of -1.0V relative to the mercurous sulfate reference electrode for 10-30 minutes; after electroplating, it is ultrasonically cleaned 3 times, and the treated grid is placed in a 150℃ drying oven for 2-3 hours before being taken out.

[0019] The lead powder in the positive electrode lead paste has an oxidation degree of 65% to 80%; the short fibers in the positive electrode lead paste are either polyacrylonitrile or polyester fiber.

[0020] The soluble lead salt is one or two of PbNO3, Pb(CH3COO)2, and PbCl2.

[0021] The dendritic lead sulfate is prepared by the following method:

[0022] 1) An apparatus using a three-way tube connected to a Buchner funnel via a peristaltic pump. One inlet of the three-way tube contains a soluble lead salt, and the other inlet contains a mixed solution of (NH4)2SO4 and polyethylene glycol PEG-2000. The outlet tube of the three-way tube is connected to the Buchner funnel after passing through the peristaltic pump. The reaction is carried out by vacuum filtration at room temperature. The molar ratio of soluble lead salt to (NH4)2SO4 is 0.8~1.

[0023] 2) Wash the filtered solid with clean water using ultrasonic cleaning at least 3 times;

[0024] 3) After cleaning, place the solid in a vacuum drying oven at 60~80℃ and dry for 2~4 hours.

[0025] The electrolyte has an electrolyte additive concentration of 0.05~0.4 mol / L.

[0026] The novel energy storage battery provided by this invention adopts a structure with opposite terminals and a busbar, fully considering the problems of acid stratification and uneven utilization of active materials in the upper and lower parts caused by excessively high plate height, which leads to reduced lifespan. This results in a more uniform current distribution and significantly improved charge acceptance and deep cycle life. The positive plate grid alloy is made of pure lead, with a corrosion resistance life of at least 20 years. The alloy is pretreated by electroplating, avoiding the problems of difficult formation of a pure lead corrosion layer and insufficient adhesion with lead paste, thus improving the battery's conductivity and deep cycle life. The positive electrode formulation incorporates pore-forming agents (nano-silica gel aqueous solution, expanded graphite) and conductive agents (tin dioxide, expanded graphite) to balance capacity and lifespan. The negative electrode formulation uses a dendritic lead sulfate formulation. The dendritic lead sulfate significantly increases the pore size and total pore volume of the negative electrode after formation, enhancing ion transport channels during charge and discharge, improving the utilization rate of negative active materials and fast charging capability, and delaying battery sulfation. The use of a high-carbon formulation for the negative electrode also contributes to improved charge acceptance. Meanwhile, if conventional lead powder is used as the main material in the high-carbon formulation, overcharging of the negative electrode can occur after battery assembly, leading to the expansion and shedding of the foamed active material in the negative electrode, rendering the battery unusable. Using dendritic lead sulfate avoids this overcharging phenomenon in the negative electrode formation, ensuring the integrity of the negative electrode structure. Compared to traditional lead-acid energy storage batteries, the horizontal energy storage battery formulation provided by this invention extends the lifespan by at least 50%. Attached Figure Description

[0027] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0028] Figure 1 This is the front view of the present invention.

[0029] Figure 2 yes Figure 1 The left view.

[0030] Figure 3 yes Figure 1 The right view. Detailed Implementation

[0031] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The following description of at least one exemplary embodiment is merely illustrative and is in no way intended to limit the present invention or its application or use. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0032] Techniques, methods, and equipment known to those skilled in the art may not be discussed in detail, but where appropriate, such techniques, methods, and equipment should be considered part of the specification.

[0033] like Figure 1 As shown, 1 is the positive terminal, 2 is the negative terminal, 3 is the positive busbar, 4 is the negative busbar, 5 is the battery case, 6 is the electrode plate, 7 is the positive electrode lug, and 8 is the negative electrode lug. The novel energy storage battery structure provided by this invention is a 2V horizontal structure, including a battery case 5, a positive terminal 1, and a negative terminal 2. The battery case 5 contains an electrolyte and electrode groups immersed in the electrolyte. The electrode groups are composed of multiple positive electrode plates and multiple negative electrode plates arranged alternately with separators. The positive electrode plate includes a positive electrode grid and positive electrode paste coated on the positive electrode grid. The negative electrode plate includes a negative electrode grid and negative electrode paste coated on the negative electrode grid. A positive busbar 3 and a negative busbar 4 are provided on the electrode groups. The positive busbar 3 and the negative busbar 4 connect all the positive electrode lugs 7 and negative electrode lugs 8 of each electrode group. Positive busbar 3 and negative busbar 4 are connected to positive terminal 1 and negative terminal 2, respectively. In this invention, positive terminal 1 and negative terminal 2 are provided on the left and right sides of the battery compartment 5. Positive terminal 1 and negative terminal 2 are respectively provided on the opposite side walls of the battery compartment 5, and in order to increase the uniformity of current distribution, separate busbars are designed on both sides.

[0034] The positive electrode plate used in this invention has a length and width dimension greater than 2. The negative electrode plate has a length and width dimension greater than 2.

[0035] In this invention, the positive terminal 1 is located at the lower part of one side wall of the battery compartment 5, and the negative terminal 1 is located at the upper part of the opposite side wall of the battery compartment 5. By using positive and negative terminals on different sides, the current flow is changed, and the utilization rate of active materials is more uniform. In conventional batteries, the utilization rate of active materials is generally higher closer to the terminal and lower further away from the terminal. Depending on the battery design capacity, multiple positive and negative terminals can be designed.

[0036] like Figure 2 , Figure 3As shown, in this embodiment, there are two positive terminals 1 and two negative terminals 2. There are two positive busbars 3: a lower positive busbar connected to the positive terminal 1 and an upper positive busbar connected to the lower positive busbar. There are two negative busbars 4: an upper negative busbar connected to the negative terminal 2 and a lower negative busbar connected to the upper negative busbar. This invention, by adding additional positive and negative busbars on both sides, avoids the situation where the utilization rate of active material far from the terminals is low due to an excessively high electrode design, effectively extending its lifespan.

[0037] Example 1

[0038] A novel energy storage battery has a 2V horizontal structure with positive and negative terminals on the left and right sides, respectively, and the length of the plates is 2.1 times their width.

[0039] The positive grid of this energy storage battery uses pure lead alloy produced by continuous stamping. Because it is difficult for the pure lead alloy to form a conductive layer during the plate solidification process, the pure lead grid needs to be electroplated to give its surface a dendritic or lamellar array structure. The electroplating process for the positive grid is as follows:

[0040] (1) The electroplating solution is composed of the following raw materials by weight percentage: 0.38% SnCl2, 0.72% PbCl2, 1.18% Na3C6H5O7, 0.05% polyethylene glycol PEG-2000, and the balance is water.

[0041] (2) Immerse the positive electrode grid in the electroplating solution and polarize it for 15 minutes at a potential of -1.0V (compared to the mercurous sulfate reference electrode).

[0042] (3) After electroplating, ultrasonic cleaning is performed 3 times. The treated grid is placed in a 150℃ drying oven for 2 hours and then taken out for use.

[0043] The positive electrode lead paste formula consists of the following raw materials by weight percentage: short fiber 0.06%, pure water 14%, 1.38 g / cm³. 3 The composition consists of 10% sulfuric acid solution, 0.06% antimony trioxide, 0.04% tin dioxide, 0.05% nano-silica gel aqueous solution, 0.02% expanded graphite, and the remainder is lead powder with an oxidation degree of 72%. The short fibers used are polyacrylonitrile.

[0044] The negative electrode grid is made of PbCaSnAl alloy using a continuous stamping process.

[0045] The negative electrode lead paste is formulated using dendritic lead sulfate instead of conventional lead powder. The preparation method for dendritic lead sulfate is as follows:

[0046] (1) A peristaltic pump connected to a Buchner funnel was used to react 99.99% by weight of soluble lead salts Pb(CH3COO)2 and (NH4)2SO4 with 0.01% polyethylene glycol PEG-2000 under vacuum filtration at room temperature. The molar ratio of soluble lead salts to (NH4)2SO4 was 0.8. Specifically, a peristaltic pump and a three-way tube were connected to the Buchner funnel. One end of the tube contained soluble lead salts, and the other end contained a mixed solution of (NH4)2SO4 and polyethylene glycol PEG-2000. After passing through the peristaltic pump, the solution was connected to the Buchner funnel and reacted under vacuum filtration at room temperature.

[0047] (2) The filtered solid was ultrasonically washed 4 times with clean water.

[0048] (3) After cleaning, place the solid in a vacuum drying oven at 60°C and dry for 2 hours.

[0049] The negative electrode lead paste formulation consists of the following raw materials by weight percentage: 16% pure water, 0.1% expanded graphite, and BET of 300~375 m. 2 / g carbon black 0.8%, barium sulfate 1.2%, lignin sulfonate 0.4%, short fiber 0.04%, the remainder being dendritic lead sulfate prepared above.

[0050] The electrolyte concentration of the energy storage battery is 1.285 g / cm³. 3 Sulfuric acid solution containing 0.05 mol / L potassium sulfate as an electrolyte additive.

[0051] Example 2

[0052] A novel energy storage battery has a 2V horizontal structure, with the positive and negative terminals on the left and right sides, respectively. The length of the plates is twice the width.

[0053] The positive electrode grid of this energy storage battery is made of pure lead alloy using a continuous stamping process. The electroplating process for the positive electrode grid is as follows:

[0054] (1) The electroplating solution is composed of the following raw materials by weight percentage: 0.76% SnCl2, 4.16% PbCl2, 1.18% Na3C6H5O7, 0.06% polyethylene glycol PEG-2000, and the balance is water.

[0055] (2) Immerse the positive electrode grid in the electroplating solution and polarize it for 30 minutes at a potential of -1.0V (compared to the mercurous sulfate reference electrode).

[0056] (3) After electroplating, ultrasonic cleaning is performed 3 times. The treated grid is placed in a 150℃ drying oven for 3 hours and then taken out for use.

[0057] The positive electrode lead paste formula consists of the following raw materials by weight percentage: short fiber 0.1%, pure water 12%, 1.38 g / cm³. 3 The composition consists of 8% sulfuric acid solution, 0.07% antimony trioxide, 0.07% tin dioxide, 0.06% nano-silica gel aqueous solution, 0.03% expanded graphite, and the remainder is lead powder with an oxidation degree of 75%. The short fibers used are polyacrylonitrile.

[0058] The negative electrode grid is made of PbCaSnAl alloy using a continuous stamping process.

[0059] The negative electrode lead paste is formulated using dendritic lead sulfate instead of conventional lead powder. The preparation method for dendritic lead sulfate is as follows:

[0060] (1) Using a device connected to a peristaltic pump and a Buchner funnel, 99.99% by weight of soluble lead salts (PbNO3 and Pb(CH3COO)2) and (NH4)2SO4 were reacted with 0.01% polyethylene glycol PEG-2000 under vacuum filtration at room temperature. The molar ratio of soluble lead salts to (NH4)2SO4 was 1.

[0061] (2) The filtered solid was ultrasonically washed 5 times with clean water.

[0062] (3) After cleaning, place the solid in a vacuum drying oven at 70°C and dry for 3 hours.

[0063] The negative electrode lead paste formulation consists of the following raw materials by weight percentage: 16% pure water, 0.2% expanded graphite, and BET of 300~375 m. 2 / g carbon black 0.75%, barium sulfate 1.0%, lignin sulfonate 0.3%, short fiber 0.06%, the remainder being dendritic lead sulfate prepared above.

[0064] The electrolyte concentration of the energy storage battery is 1.295 g / cm³. 3 A sulfuric acid solution containing electrolyte additives: potassium sulfate and lithium sulfate, with a molar concentration of 0.1 mol / L for the electrolyte additives.

[0065] Comparative Example

[0066] The existing 2V horizontal energy storage battery uses conventional plates with an aspect ratio of 1.1; its positive electrode lead paste is composed of the following raw materials by weight percentage: short fibers 0.06%~0.1%, pure water 9%~14%, 1.38g / cm³ 3 The solution contains 7%–12% sulfuric acid, 0.5%–1.0% 4BS, 5%–16% red lead, and the remainder is lead powder. Both the positive and negative electrode grids are made of PbCaSnAl alloy using gravity casting. The negative electrode lead paste is composed of the following raw materials by weight percentage: 12%–16% pure water, 1.38 g / cm³... 3Sulfuric acid solution 6%~12%, carbon black 0.1~1.0%, BET 75~200 m 2 The electrolyte contains 0.6-1.0% barium sulfate, 0.2-0.4% lignin sulfonate, 0.04%-0.08% short fibers, and the remainder is lead powder. The electrolyte density is 1.28-1.32 g / cm³. 3 The sulfuric acid solution contains sodium sulfate as an electrolyte additive, with a molar concentration of 0.06~0.14 mol / L.

[0067] The lifetime cycle counts for the comparative and example cases are shown in the table below.

[0068] Comparative Example Example 1 Example 2 70% of DOD cycle count 2800 4500 4800 Increase / 60% 71%

[0069] The above description is merely an exemplary embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. An energy storage battery, comprising a battery tank (5), a positive terminal (1), a negative terminal (2); an electrolyte is arranged in the battery tank, and a pole group is immersed in the electrolyte; the pole group is formed by alternately arranging a plurality of positive plates and a plurality of negative plates with a separator; the positive plate comprises a positive plate grid and a positive lead paste coated on the positive plate grid; the negative plate comprises a negative plate grid and a negative lead paste coated on the negative plate grid; a positive busbar (3) and a negative busbar (4) are arranged on the pole group; the positive busbar (3) and the negative busbar (4) are respectively connected with the positive terminal (1) and the negative terminal (2) through connecting all the positive plate tabs and the negative plate tabs of each pole group; characterized in that: the length-width ratio of the positive plate is greater than or equal to 2; the length-width ratio of the negative plate is greater than or equal to 2; the positive terminal (1) and the negative terminal (2) are respectively arranged on the opposite two side walls of the battery tank (5); the positive plate grid is made of pure lead alloy through a continuous punching process and is subjected to electroplating treatment through the following steps: soaking the positive plate grid in an electroplating solution, cleaning and drying after electroplating; the electroplating solution is composed of the following raw materials in percentage by weight: 0.19%-0.76% SnCl2, 0.72%-4.17% PbCl2, 0.77%-1.29% Na3C6H5O7 and 0.02-0.06% polyethylene glycol PEG-2000, and the balance is water; the negative plate grid is made of PbCaSnAl alloy through a continuous punching process; the dendritic lead sulfate is prepared by vacuum filtration of soluble lead salt, (NH4)2SO4 and 0.01% polyethylene glycol PEG-2000 at room temperature; the molar ratio of the soluble lead salt to (NH4)2SO4 is 0.8-1; the positive terminal (1) is located at the lower part of one side wall of the battery tank (5), and the negative terminal (2) is located at the upper part of the opposite side wall of the battery tank (5). There are a plurality of positive terminals (1) and a plurality of negative terminals (2). There are two positive terminals (1) and two negative terminals (2). There are two positive busbars (3), which are a lower positive busbar connected with the positive terminal (1) and an upper positive busbar connected with the lower positive busbar. There are two negative busbars (4), which are an upper negative busbar connected with the negative terminal (2) and a lower negative busbar connected with the upper negative busbar. The positive lead paste is composed of raw materials with the following weight percentages: short fibers 0.06%-0.1%, pure water 10%-15%, 1.38g / cm 3 sulfuric acid solution 8%-11%, antimony trioxide 0.04%-0.1%, tin dioxide 0.02%-0.08%, nano-silica colloidal aqueous solution 0.05%-0.1%, expanded graphite 0.02%-0.04%, and the rest is lead powder; The positive plate grid electroplating treatment is specifically: soaking the positive plate grid in the electroplating solution, and polarizing at a potential of -1.0 V compared with a mercurous sulfate reference electrode for 10-30 min; after electroplating, ultrasonic cleaning is performed for 3 times, and the treated plate grid is placed in a 150℃ drying box for 2-3 h and then taken out. The negative lead paste is composed of raw materials with the following weight percentages: pure water 12%~16%, expanded graphite 0.1~0.4%, BET 300~375 m 2 / g carbon black 0.4~0.8%, barium sulfate 0.8~1.2%, lignin sulfonate 0.2~0.5%, short fiber 0.04%~0.08%, and the rest is dendritic lead sulfate; The oxidation degree of lead powder in the positive lead paste is 65%-80%; the short fibers in the positive lead paste are one of polyacrylonitrile and polyester fibers. The electrolyte is made of 1.26~1.30g / cm 3 The electrolyte is made of 1.26~1.30g / cm The electrolyte is made of 1.26~1.30g / cm 2. The energy storage cell of claim 1, wherein: The soluble lead salt is one or two of PbNO3, Pb(CH3COO)2 and PbCl2.

3. The energy storage cell of claim 1 or 2, wherein: The dendritic lead sulfate is prepared by the following method:

4. The energy storage cell of claim 1 or 2, wherein: ​ 5. The energy storage cell of claim 4, wherein: ​ ​ 6. The energy storage cell of claim 1, wherein: ​ 7. The energy storage cell of claim 1, wherein: ​ 8. The energy storage cell of claim 1, wherein: ​ 9. The energy storage cell of claim 1, wherein: ​ 1) using a three-way pipe through peristaltic pump connected in the device of Buchner funnel, three-way pipe in one of the feeding hose for soluble lead salt, another feeding hose for (NH4)2SO4 and polyethylene glycol PEG-2000 mixed solution, three-way pipe discharge pipe through peristaltic pump after connecting Buchner funnel, vacuum filtration at room temperature to carry out the reaction; wherein, the molar ratio of soluble lead salt and (NH4)2SO4 is 0.8~1; 2) the filtered solid is washed with clean water for at least 3 times or more; 3) after washing, the solid is placed in a vacuum drying oven at 60~80℃ for 2~4h.

10. The energy storage cell of claim 1, wherein: In the electrolyte, the molar concentration of electrolyte additive is 0.05~0.4mol / L.

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