Energy storage battery and production process thereof

Abstract

The invention discloses an energy storage battery and a production process thereof, and belongs to the technical field of solar energy storage batteries. The main body structure comprises a battery shell, a cover plate is packaged at the top of the battery shell, battery terminals are mounted on two sides in the cover plate, positive plates and negative plates are respectively arranged in an inner cavity of the battery shell, and the positive plates and the negative plates are alternately arranged. Through a three-dimensional wave structure, the contact area between a positive plate and an electrolyte and the contact area between a negative plate and the electrolyte are increased, the oxidation-reduction reaction rate is increased, then grid alloy components and a positive electrode lead paste formula are optimized, a lead-calcium-tin-aluminum system is utilized, grid corrosion is inhibited, a conductive wire is improved, meanwhile, grains are refined, microcracks are reduced, and the service life of the battery is prolonged. The creep resistance of the alloy is enhanced, the capacity recovery rate and the cycle life of the battery after deep discharge are improved, and the performance of the battery is optimized.

Description

Technical Field

[0001] The present invention relates to the technical field of solar energy storage batteries, in particular to an energy storage battery and a production process thereof. Background Art

[0002] Solar batteries are the application of "batteries" in solar photovoltaic power generation. Four types of batteries are used: maintenance-free lead-acid batteries, standard lead-acid batteries, gel batteries, and alkaline nickel-cadmium batteries. The most widely used solar batteries in China are primarily maintenance-free lead-acid batteries and gel batteries. These two types of batteries, due to their inherent "no" maintenance and minimal environmental impact, are well-suited for reliable solar power systems, particularly for unmanned workstations.

[0003] Solar energy storage batteries need to provide continuous power in the absence of sunlight, such as providing energy for street lights. However, when the mains supply is insufficient or there is continuous rainy weather, the battery is prone to long-term deep discharge (discharge depth > 80%), leading to the following problems:

[0004] Defects of traditional grid alloys:

[0005] Conventional lead-calcium alloys (such as Pb-Ca-Sn) have an insufficient tin content (usually <1wt%), which causes irreversible sulfation of the grid after deep discharge, destroying the lattice structure and reducing the electron transfer efficiency.

[0006] Failure of the active material in the positive lead paste:

[0007] Traditional lead paste formulas lack anti-sulfurization ingredients (such as antimony trioxide and stannous sulfate). The active substance (PbO2) is difficult to restore after being converted into PbSO4 at high discharge rates, and the capacity recovery rate is less than 85%.

[0008] Process parameter limitations:

[0009] The existing paste temperature (<70°C) and curing conditions (short-term high-temperature stage) cannot fully activate the effects of additives in the lead paste, resulting in low plate porosity (<45%) and poor electrolyte permeability. Summary of the Invention

[0010] The object of the present invention is to provide an energy storage battery and its production process. By redesigning the outer surface structure of the electrode plate and adopting a three-dimensional wavy surface, the contact area between the positive electrode plate and the negative electrode plate and the electrolyte is increased. At the same time, the grid alloy composition (lead-calcium-tin-aluminum system) and the positive electrode lead paste formula (containing antimony trioxide, stannous sulfate, etc.) are optimized. Combined with high temperature and paste and multi-stage curing process, the capacity recovery rate and cycle life of the battery after deep discharge are significantly improved, so as to solve the problems raised in the above background technology.

[0011] To achieve the above objectives, the present invention provides the following technical solution: an energy storage battery, comprising:

[0012] Main structure;

[0013] The main structure includes a battery housing, a cover plate is encapsulated on the top of the battery housing, battery terminals are installed on both sides of the cover plate, and the inner cavity of the battery housing is respectively provided with a positive electrode plate and a negative electrode plate, the positive electrode plates and the negative electrode plates are alternately arranged, and the positive electrode plates and the negative electrode plates are respectively connected to the battery terminals via connectors, the surface of the positive electrode plate is wavy, and the surface of the negative electrode plate facing the positive electrode plate remains parallel;

[0014] The main structure also includes electrolyte filled into the inner cavity of the battery shell.

[0015] Preferably, the inner cavity of the battery housing is provided with a limit card slot, and the outer sides of the positive plate and the negative plate are fixed with a limit card block, and the limit card block is clamped in the limit card slot.

[0016] Based on an energy storage battery, a production process of an energy storage battery is also provided, comprising the following steps:

[0017] S1. Material selection: Choose a suitable battery shell;

[0018] S2. Preparation of positive and negative electrode grids

[0019] (1) Preparation of positive electrode grid

[0020] The alloy used for the positive electrode grid is a lead-calcium alloy, which includes the following raw materials: calcium, tin, aluminum and lead, and the weight percentage of each raw material is: calcium 0.075-0.09wt%, tin 1.25-2.25wt%, aluminum 0.02-0.06wt%, and the rest is metallic lead. The positive electrode grid materials are mixed and melted and processed into the grid shape;

[0021] (2) Preparation of negative electrode grid

[0022] S3. Preparation of positive and negative electrode lead pastes

[0023] (1) Preparation of positive electrode lead paste

[0024] Material preparation

[0025] The raw materials include: antimony trioxide, potassium sulfate, stannous sulfate, colloidal graphite, paste acid, formula water, recycled powder, short fiber and lead powder;

[0026] The weight percentages of the various raw materials are as follows: antimony trioxide 0.1-0.3wt%, potassium sulfate 0.2-0.3wt%, stannous sulfate 0.3-0.5wt%, colloidal graphite 0.1-0.3wt%, sylvite 10-13wt%, formula water 9-10wt%, recycled powder 3-5wt%, short fiber 0.08-0.1wt%, and the rest is lead powder with an oxidation degree of 72-77%.

[0027] Preparation before ointment

[0028] The raw materials are screened, cleaned, dried, weighed, and then ground in sequence;

[0029] Paste processing

[0030] Add various raw materials into the paste machine in sequence and stir and mix them to form a paste mixture;

[0031] Positive plate processing

[0032] Apply the paste on the grid and then cure it at high temperature.

[0033] to process;

[0034] (2) Preparation of negative electrode lead paste

[0035] S4. Install the processed positive and negative plates inside the battery housing, then inject electrolyte, and seal the cover plate on the top of the battery housing;

[0036] S5. Perform charging and discharging tests on the assembled energy storage battery.

[0037] Preferably, the lead-calcium alloy is prepared in S2, and the various raw materials are first weighed according to the mass ratio of different raw materials, and then the raw materials are added into the furnace, and the furnace is continuously processed to melt and mix the various raw materials, and the liquid mixed metal is filtered and poured into the mold to form a metal plate or a grid structure, and then the metal plate is machined, or directly polished using the grid structure.

[0038] Preferably, the furnace smelting temperature in S2 is 450-480°C, argon gas is introduced for protection, and a liquid alloy solution is formed. Then, during the pouring process, cooling intervention is performed, and the cooling rate is maintained at 10-15°C / min to obtain a uniform α-Pb solid solution structure.

[0039] Preferably, the recycled powder in S3 is sieved through 200 mesh, the short fibers are polyester fibers, the length of which is maintained at 0.5-1 mm, and the PbO content in the lead powder is ≥70%.

[0040] Preferably, when processing S3 and the paste, the raw material addition is divided into three stages:

[0041] (1) Dry mixing stage

[0042] Main solid raw materials: lead powder, antimony trioxide, potassium sulfate, stannous sulfate, recycled powder,

[0043] Add the solid raw materials into the paste mixing machine and mix thoroughly;

[0044] (2) Wet mixing stage

[0045] Add water first: add 10%-13% of the total weight of the dry mixed raw materials with deionized water and stir for 10 minutes to ensure the initial moistening of the materials;

[0046] Post-acidification: Slowly add acid (H2SO4, density 1.25g / cm 3 ), the dosage is 8%-10% of the dry mixed raw materials, and the acid addition time is controlled at 10-15 minutes;

[0047] Special additives: colloidal graphite is added, usually at the same time as lead powder, and short fibers are added in the later stage of wet mixing;

[0048] (3) Final mixing stage

[0049] Add the remaining deionized water and lead paste acid into the paste mixer in turn and stir until the lead paste temperature drops below 45 degrees to ensure a stable reaction.

[0050] Preferably, the highest temperature of the lead paste during the lead paste processing in S3 is 74-76° C., and the high temperature duration is controlled to be 3-5 minutes.

[0051] Preferably, the S3 positive plate lead paste is cured in three stages: the first stage is at 75°C for 9-10 hours, the second stage is at 60°C for 12 hours, and the third stage is dried at room temperature for 24 hours.

[0052] Preferably, a comparative example is added in the S5 charge and discharge test, and different lead paste formula ratios are compared with the traditional formula ratio.

[0053] Compared with the prior art, the present invention has the following beneficial effects:

[0054] 1. The present invention redesigns the shape of the positive and negative plates and increases the contact area between the positive and negative plates and the electrolyte through a three-dimensional wavy structure, thereby improving the redox reaction rate. Subsequently, the grid alloy composition and the positive electrode lead paste formula are optimized, and the lead-calcium-tin-aluminum system is used to inhibit grid corrosion and improve conductive lines. At the same time, the grain size is refined, microcracks are reduced, the creep resistance of the alloy is enhanced, and the capacity recovery rate and cycle life of the battery after deep discharge are improved, thereby optimizing the battery performance.

[0055] 2. The present invention improves the performance of the positive electrode plate and the battery capacity after full discharge by improving the composition, ratio and preparation process of the positive electrode plate. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] Figure 1 It is a schematic diagram of the three-dimensional structure of the main structure of the energy storage battery of the present invention;

[0057] Figure 2 This is a schematic diagram of the disassembled three-dimensional structure of the main structure of the energy storage battery of the present invention;

[0058] Figure 3 It is a schematic diagram of the three-dimensional structure of the positive plate and the negative plate of the present invention.

[0059] Numbers in the figure: 1. Battery casing; 2. Cover; 3. Battery terminal; 4. Positive plate; 5. Negative plate; 6. Connector; 7. Limiting slot; 8. Limiting block. DETAILED DESCRIPTION

[0060] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0061] The present invention provides Figures 1 to 3 An energy storage battery is shown, comprising:

[0062] Main structure;

[0063] The main structure includes a battery housing 1, the top of which is encapsulated with a cover plate 2, and battery terminals 3 are installed on both sides of the cover plate 2. The inner cavity of the battery housing 1 is respectively provided with positive plates 4 and negative plates 5, which are arranged alternately. The positive plates 4 and negative plates 5 are respectively connected to the battery terminals 3 through connectors 6. The surface of the positive plate 4 is wavy, and the surface of the negative plate 5 facing the positive plate 4 remains parallel.

[0064] The main structure also includes an electrolyte perfused into the inner cavity of the battery housing 1;

[0065] Through the three-dimensional wave plate design:

[0066] After 200 cycles, the crack density is reduced to <3 / cm 2 (Traditional structure>15 / cm 2 );

[0067] Active material utilization is increased by 12% (by increasing the reaction surface area).

[0068] The surfaces of the positive plate 4 and the negative plate 5 are wavy (wavelength 4-6 mm, wave height 1.2-1.8 mm). The stress distribution is optimized through finite element simulation. The peaks of the wavy structure on the positive plate 4 correspond to the troughs of the wavy structure on the negative plate 5.

[0069] A gradient thinning area is set at the edge of the plate (the thickness gradually changes from 2.0mm in the center to 1.2mm at the edge) to relieve expansion stress.

[0070] At the same time, optimize the grid skeleton structure:

[0071] Central area, diamond grid (grid size 3x3mm 2 ) Improve mechanical support strength, compressive strength> 80Pa;

[0072] In the edge area, radial ribs (rib width 0.8-1.2mm) suppress plate deformation (plate warpage after cycling <0.5mm / m);

[0073] The grid skeleton is made of lead alloy, and then the surface of the lead alloy is coated with a conductive polymer layer (thickness 20-50μm) to reduce the cross-sectional resistance (contact resistance <0.1mΩ·cm 2 ).

[0074] Battery terminal 3 is a copper-aluminum composite terminal with a thermal conductivity greater than 350350 W / m·K. A micro heat pipe with a diameter of 2 mm is embedded inside and filled with acetone as a working fluid to achieve rapid thermal equalization and maintain the temperature difference within 2°C.

[0075] The table shows the technical effects and comparative data.

[0076] Performance indicators Structure of the present invention Traditional structure Cycle life (DOD100%) 620 times (capacity>80%) 200 times (capacity < 70%) Plate crack density <![CDATA[2.8 lines / cm 2 > <![CDATA[16.3 lines / cm 2 > Temperature uniformity ΔT=1.5℃ ΔT=8.2℃ Acid concentration gradient <![CDATA[0.08g / cm 3 ]]> <![CDATA[0.92g / cm 3 ]]>

[0077] like Figure 2 As shown,

[0078] The inner cavity of the battery casing 1 is provided with a limit card slot 7, and the outer side of the positive plate 4 and the negative plate 5 is fixed with a limit card block 8, which is engaged in the limit card slot 7. By providing the limit card slot 7 in the inner cavity of the battery casing 1, the positive plate 4 and the negative plate 5 are limited by the limit card block 8 to prevent the positive plate 4 and the negative plate 5 from contacting each other.

[0079] Based on an energy storage battery, a production process of an energy storage battery is also provided, comprising the following steps:

[0080] S1. Material selection: Select a suitable battery shell 1;

[0081] S2. Preparation of positive and negative electrode grids

[0082] (1) Preparation of positive electrode grid

[0083] The alloy used for the positive electrode grid is a lead-calcium alloy, which includes the following raw materials: calcium, tin, aluminum and lead, and the weight percentage of each raw material is: calcium 0.075-0.09wt%, tin 1.25-2.25wt%, aluminum 0.02-0.06wt%, and the rest is metallic lead, and the purity of the metallic lead is ≥99.99%. The positive electrode grid materials are mixed and melted and processed into a grid shape;

[0084] Calcium is preferably 0.08 wt % to enhance the creep resistance of the alloy. The fine and evenly distributed grain structure can increase the grain boundary area, hinder dislocation movement, and improve creep resistance. At the same time, the presence of the precipitate phase can also effectively hinder dislocation movement and improve creep resistance.

[0085] Tin is preferably 1.8wt%, which inhibits grid corrosion and improves conductivity, effectively improving the corrosion resistance of the electrolyte to the lead-calcium alloy grid, thereby enhancing the strength of the plate;

[0086] Aluminum is preferably 0.04wt% to refine the grains, reduce the generation of microcracks, and improve the creep resistance of the alloy.

[0087] (2) Preparation of negative electrode grid

[0088] The negative electrode grid uses the traditional negative electrode grid composition and structure.

[0089] After deep discharge, conventional lead-calcium alloy grids crack at the grid-active material interface due to stress concentration and oxidation reactions, further accelerating the shedding of active materials (experiments show that the active material loss rate of conventional grids is >10% after 20 cycles). The use of an improved positive grid formula and structure can effectively increase the reversible conversion rate of PbSO4 in the plate (greater than 95%, compared to <70% for conventional ones);

[0090] Under DOD 100%, the improved battery has a cycle life of more than 500 times and a capacity retention rate of more than 80%, far exceeding the traditional battery's cycle life of less than 200.

[0091] S3. Preparation of positive and negative electrode lead pastes

[0092] (1) Preparation of positive electrode lead paste

[0093] Material preparation

[0094] The raw materials include: antimony trioxide, potassium sulfate, stannous sulfate, colloidal graphite, paste acid, formula water, recycled powder, short fiber and lead powder;

[0095] The weight percentages of the various raw materials are as follows: antimony trioxide 0.1-0.3wt%, potassium sulfate 0.2-0.3wt%, stannous sulfate 0.3-0.5wt%, colloidal graphite 0.1-0.3wt%, sylvite 10-13wt%, formula water 9-10wt%, recycled powder 3-5wt%, short fiber 0.08-0.1wt%, and the rest is lead powder with an oxidation degree of 72-77%.

[0096] Antimony trioxide can inhibit the growth of PbSO4 crystals; potassium sulfate improves the ionic conductivity of the electrolyte, and stannous sulfate promotes the reduction reaction of PbO2; colloidal graphite helps to strengthen the conductive network of the plate; and paste acid (H2SO4, density 1.25g / cm 3 ) Control the acidity of the lead paste; Formula water to adjust the fluidity of the lead paste to facilitate paste processing, while maintaining the water content of the plate to avoid a decrease in the water content of the plate, which may lead to microcracks; Recycled powder is used as a filler to reduce costs, and short fibers are used to improve the mechanical strength of the plate; At the same time, there is no need to use expensive additives (such as carbon nanotubes), and the cost is 50% lower than that of lithium battery solutions. Due to the introduction of recycled powder, lead pollution is reduced. At the same time, the improved lead-acid battery production line is compatible with existing production lines, and only the alloy melting and solidification process parameters need to be adjusted.

[0097] Preparation before ointment

[0098] The raw materials are screened, cleaned, dried, and weighed, and then ground in sequence. The raw materials are screened individually using screens of different specifications, and impurities in the raw materials are removed. The solid raw materials are then heated and dried, and then naturally cooled to return to room temperature. In the weighing process, multiple people are used to weigh the materials to avoid errors caused by one person weighing.

[0099] Paste processing

[0100] Add various raw materials into the paste machine in sequence and stir and mix them to form a paste mixture;

[0101] Processing of positive plate 4

[0102] The paste is applied to the grid and then cured at high temperature.

[0103] shape to process;

[0104] (2) Preparation of negative electrode lead paste

[0105] The composition, proportion and preparation process of traditional negative electrode lead paste are used.

[0106] S4. Install the processed positive electrode plate 4 and negative electrode plate 5 inside the battery housing 1, then inject electrolyte, and seal the cover plate 2 on the top of the battery housing 1.

[0107] The main improvements of the improved energy storage battery are: adjustment of the composition and ratio of the positive electrode grid, adjustment of the composition, ratio and preparation process of the positive electrode lead paste; after the improvement, compared with traditional lead-acid batteries, the capacity recovery ability after deep discharge is significantly improved, and the number of cycles is greatly improved.

[0108] The lead-calcium alloy is prepared in S2. First, various raw materials are weighed according to the mass ratio of different raw materials, and then the raw materials are added into the furnace. The furnace is continuously processed to melt and mix the various raw materials, and the liquid mixed metal is filtered and poured into the mold to form a metal plate or grid structure. The metal plate is machined or directly polished using the grid structure. By preparing the lead-calcium alloy according to the ratio and using the lead-calcium alloy to process the electrode grid, it is possible to avoid direct casting of the grid and internal defects, which helps to improve the quality of the grid. The outer surface of the grid can be finely processed by the machine tool to meet the different shapes and structures of the grid, while maintaining the uniformity of the strength of the different structures of the grid.

[0109] The melting temperature of the furnace in S2 is 450-480°C, and argon gas is introduced for protection to form a liquid alloy solution. Subsequently, during the pouring process, cooling intervention is performed to maintain a cooling rate of 10-15°C / min to obtain a uniform α-Pb solid solution structure. By controlling the temperature, it is possible not only to ensure the melting and mutual fusion of all raw materials and uniform distribution of different raw materials, but also to control the cooling rate to maintain stability of the internal stress of the lead-calcium alloy and avoid excessively fast cooling, which may cause fine cracks in the lead-calcium alloy due to uneven stress and affect the strength of the lead-calcium alloy.

[0110] The recycled powder in S3 is sieved through 200 meshes, the short fibers are polyester fibers, and the length is maintained at 0.5-1 mm. The PbO content in the lead powder is ≥70%.

[0111] When processing the S3 paste, the raw material addition is divided into three stages:

[0112] (1) Dry mixing stage

[0113] Main solid raw materials: lead powder, antimony trioxide, potassium sulfate, stannous sulfate, recycled powder,

[0114] Add the solid raw materials into the paste mixing machine and mix thoroughly;

[0115] (2) Wet mixing stage

[0116] Add water first: add 10%-13% of the total weight of the dry mixed raw materials with deionized water and stir for 10 minutes to ensure the initial moistening of the materials;

[0117] Post-acidification: Slowly add acid (H2SO4, density 1.25g / cm 3 ), the dosage is 8%-10% of the dry mixed raw materials, and the acid addition time is controlled at 10-15 minutes;

[0118] Special additives: colloidal graphite is added, usually at the same time as lead powder, and short fibers are added in the later stage of wet mixing;

[0119] (3) Final mixing stage

[0120] Add the remaining deionized water and lead paste acid into the paste mixer in sequence, stirring until the lead paste temperature drops below 45 degrees to ensure a stable reaction.

[0121] By limiting the order of adding the raw materials to the paste, the uniformity of the solid and liquid raw materials during mixing is ensured, which prevents the raw materials from being mixed quickly in a short period of time, causing the paste to solidify at a high temperature, and making it impossible to evenly distribute the raw materials inside the lead paste, which affects the use effect of the positive electrode plate, directly affecting the charging and discharging efficiency of the battery, and indirectly affecting the battery life;

[0122] By mixing the dry materials first, it is possible to prevent the dry materials from reacting with each other in a short period of time. At the same time, when the dry materials and wet materials are mixed, the wet materials are added in small amounts and multiple times to facilitate the control of the reaction rate, avoid rapid temperature rise, and make it impossible to control the temperature of the paste, thereby affecting the preparation of the lead paste.

[0123] The maximum temperature of the lead paste during the lead paste processing in S3 is 74-76° C., and the high temperature duration is controlled to be 3-5 minutes, so as to fully activate the additives added to the lead paste and avoid low plate porosity, which leads to poor electrolyte permeability.

[0124] The S3 positive plate 4 lead paste is cured in three stages: the first stage is at 75°C for 9-10 hours, the second stage is at 60°C for 12 hours, and the third stage is dried at room temperature for 24 hours;

[0125] Through three-stage cooling and curing, the plate porosity can be increased to 50-55%.

[0126] The compression ratio of the above-mentioned plate assembly separator is maintained at 8-19%.

[0127] In the S5 charge and discharge test, a comparative example was added to compare different lead paste formulations with the traditional formulation.

[0128] Data comparison was conducted through experiments. By comparing the improved batteries with traditional batteries, first the improved batteries all used the improved positive grid formula and ratio, and then the battery performance was tested in three embodiments.

[0129] Example 1

[0130] Lead paste ratio: antimony trioxide 0.15wt%, potassium sulfate 0.25wt%, stannous sulfate 0.3wt%, colloidal graphite 0.2wt%, synthetic acid 10wt%, formula water 9wt%, recycled powder 3wt%, short fiber 0.08wt%, and the rest is lead powder with an oxidation degree of 72-77%;

[0131] Example 2

[0132] Lead paste ratio: antimony trioxide 0.25wt%, potassium sulfate 0.2wt%, stannous sulfate 0.5wt%, colloidal graphite 0.15wt%, synthetic acid 10wt%, formula water 9wt%, recycled powder 3wt%, short fiber 0.09wt%, the rest is lead powder with an oxidation degree of 72-77%

[0133] Example 3

[0134] Lead paste ratio: antimony trioxide 0.25wt%, potassium sulfate 0.2wt%, stannous sulfate 0.5wt%, colloidal graphite 0.15wt%, synthetic acid 10wt%, formula water 9wt%, recycled powder 3wt%, short fiber 0.09wt%, and the rest is lead powder with an oxidation degree of 72-77%.

[0135] In comparison, the tin content of the grid alloy is 1.195-1,225%, the formula composition of the traditional industrial battery lead paste is 0.1%, and the short fiber is 0.1%.

[0136] Battery capacity recovery test

[0137]

[0138]

[0139] The data shows that the improved energy storage battery has a significant improvement in performance compared to traditional batteries, and the lead paste ratio is more reasonable: antimony trioxide 0.25wt%, potassium sulfate 0.2wt%, stannous sulfate 0.5wt%, colloidal graphite 0.15wt%, synthetic acid 10wt%, formula water 9wt%, recycled powder 3wt%, short fiber 0.09wt%, and the rest is lead powder with an oxidation degree of 72-77%.

[0140] Traditional lead paste formula composition (positive / negative)

[0141] 1. Positive lead paste (lead dioxide active material)

[0142]

[0143] 2. Negative lead paste (spongy lead active material)

[0144]

[0145]

[0146] Technical problems with traditional formulas

[0147] Active substance shedding:

[0148] The fiber content in the positive lead paste is low (<0.5%), and the plate vibration resistance is insufficient (vibration test shedding rate>3%);

[0149] The decomposition of the negative electrode expansion agent produces CO2, which leads to uncontrolled porosity (the porosity decreases by 40% after 100 cycles).

[0150] Increased sulfation:

[0151] The amount of barium salt added to the negative electrode is fixed, and the crystal morphology of lead sulfate cannot be dynamically adjusted (>50% PbSO4 in the traditional formula is irreversible large particles);

[0152] The sulfuric acid concentration gradient at the positive electrode causes local overcharge (the thickness of the lead sulfate layer at the electrode edge is >200μm).

[0153] Conductive network defects:

[0154] Uneven dispersion of carbon black (particle size distribution 1-50μm), broken negative electrode electron channel (conductivity <10 2 S / m);

[0155] The positive electrode lacks a nano-conductive skeleton, and the polarization voltage increases by more than 15% during high-rate discharge.

[0156] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. An energy storage battery, characterized in that: include: Main structure; The main structure comprises a battery housing (1), the top of the battery housing (1) is encapsulated with a cover plate (2), battery terminals (3) are installed on both sides of the cover plate (2), the inner cavity of the battery housing (1) is respectively provided with a positive electrode plate (4) and a negative electrode plate (5), the positive electrode plates (4) and the negative electrode plates (5) are alternately arranged, the positive electrode plates (4) and the negative electrode plates (5) are respectively connected to the battery terminals (3) via connectors (6), the surface of the positive electrode plate (4) is wavy, and the surface of the negative electrode plate (5) facing the positive electrode plate (4) remains parallel; The main structure also includes electrolyte injected into the inner cavity of the battery shell (1).

2. The energy storage battery according to claim 1, characterized in that: The inner cavity of the battery housing (1) is provided with a limit card slot (7), and the outer sides of the positive plate (4) and the negative plate (5) are fixed with a limit card block (8), and the limit card block (8) is engaged in the limit card slot (7).

3. Based on the energy storage battery according to any one of claims 1-2, a production process of the energy storage battery is further provided, characterized in that: The steps include: S1. Material selection: Choose a suitable battery shell; S2. Preparation of positive and negative electrode grids (1) Preparation of positive electrode grid The alloy used for the positive grid is lead-calcium alloy, Includes the following raw materials: calcium, tin, aluminum and lead, The mass percentages of the raw materials are as follows: calcium 0.075-0.09wt%, tin 1.25-2.25wt%, aluminum 0.02-0.06wt%, and the remainder is metallic lead. The positive electrode grid materials are mixed, melted, and processed into a grid shape. (2) Preparation of negative electrode grid S3. Preparation of positive and negative electrode lead pastes (1) Preparation of positive electrode lead paste Material preparation The raw materials include: antimony trioxide, potassium sulfate, stannous sulfate, colloidal graphite, paste acid, formula water, recycled powder, short fiber and lead powder; The weight percentages of the various raw materials are as follows: antimony trioxide 0.1-0.3wt%, potassium sulfate 0.2-0.3wt%, stannous sulfate 0.3-0.5wt%, colloidal graphite 0.1-0.3wt%, sylvite 10-13wt%, formula water 9-10wt%, recycled powder 3-5wt%, short fiber 0.08-0.1wt%, and the rest is lead powder with an oxidation degree of 72-77%. Preparation before ointment The raw materials are screened, cleaned, dried, weighed, and then ground in sequence; Paste processing Add various raw materials into the paste machine in sequence and stir and mix them to form a paste mixture; Positive plate processing The paste is applied to the grid and then cured at high temperature, and then the shape of the positive plate is processed; (2) Preparation of negative electrode lead paste S4. Install the processed positive and negative plates inside the battery housing, then inject electrolyte, and seal the cover plate on the top of the battery housing; S5. Perform charging and discharging tests on the assembled energy storage battery.

4. The production process of an energy storage battery according to claim 3, characterized in that: The lead-calcium alloy is prepared in S2. First, various raw materials are weighed according to the mass ratio of different raw materials, and then the raw materials are added into the furnace. The furnace is continuously processed to melt and mix the various raw materials, and the liquid mixed metal is filtered. The liquid metal solution is poured into a mold to form a metal plate or a grid structure. The metal plate is then machined, or the grid structure is directly used for grinding.

5. The production process of an energy storage battery according to claim 3, characterized in that: The melting temperature in the furnace in S2 is 450-480°C, and argon gas is introduced for protection to form a liquid alloy solution. Then, during the pouring process, cooling intervention is performed, and the cooling rate is maintained at 10-15°C / min to obtain a uniform α-Pb solid solution structure.

6. The production process of an energy storage battery according to claim 3, characterized in that: The recycled powder in S3 is sieved through 200 meshes, the short fibers are polyester fibers, and the length is maintained at 0.5-1 mm. The PbO content in the lead powder is ≥70%.

7. The production process of an energy storage battery according to claim 3, characterized in that: When processing the S3 paste, the raw material addition is divided into three stages: (1) Dry mixing stage Main solid raw materials: lead powder, antimony trioxide, potassium sulfate, stannous sulfate, recycled powder, Add the solid raw materials into the paste mixing machine and mix thoroughly; (2) Wet mixing stage Add water first: add 10%-13% of the total weight of the dry mixed raw materials with deionized water and stir for 10 minutes to ensure the initial moistening of the materials; Post-acidification: Slowly add acid (H2SO4, density 1.25g / cm 3 ), the dosage is 8%-10% of the dry mixed raw materials, and the acid addition time is controlled at 10-15 minutes; Special additives: colloidal graphite is added, usually at the same time as lead powder, and short fibers are added in the later stage of wet mixing; (3) Final mixing stage Add the remaining deionized water and lead paste acid into the paste mixer in turn and stir until the lead paste temperature drops below 45 degrees to ensure a stable reaction.

8. The production process of an energy storage battery according to claim 3, characterized in that: The highest temperature of the lead paste during the lead paste processing in S3 is 74-76° C., and the high temperature duration is controlled to be 3-5 minutes.

9. The production process of an energy storage battery according to claim 3, characterized in that: The S3 positive plate lead paste is cured in three stages: the first stage is at 75°C for 9-10 hours, the second stage is at 60°C for 12 hours, and the third stage is dried at room temperature for 24 hours.

10. The production process of an energy storage battery according to claim 3, characterized in that: In the S5 charge and discharge test, a comparative example was added to compare different lead paste formulations with the traditional formulation.

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