Preparation method of long-life light-weight lead-acid storage battery

Abstract

The invention discloses a long-life light-weight lead-acid storage battery, and belongs to the technical field of lead-acid storage battery manufacturing. The positive pole plate of the lead-acid storage battery is prepared by coating a Pb-Ca-Sn-Al stamping grid with positive lead plaster containing stannous mono-sulphate and antimony trioxide; the lead-acid storage battery is subjected to reverse charging before formation, Sb and Sn in lead paste are generated on the surface of a positive grid through electro-deposition, then internal formation is completed through charging and discharging, and finally large-current charging activation is conducted. In the manufacturing process of a polar plate and the forming process of an active substance, a positive electrode is converted into a negative electrode by utilizing a reverse charging electrochemical formation process, and Sb < 2 + > and Sn < 2 + > in positive electrode lead paste are subjected to a cathode electrolytic reduction reaction to generate Sb and Sn metals, so that the Sb and Sn in the positive electrode lead paste are electrodeposited on the surface of a grid in one step, then normal formation is carried out, and then high-current charging activation is carried out; the interface structure is further improved and the service life of the battery is prolonged.

Description

Technical Field

[0001] The present invention belongs to the technical field of lead - acid battery manufacturing, and particularly relates to a preparation method of a long - life lightweight lead - acid battery. Background Art

[0002] The market competition of lead - acid batteries for electric bicycles is fierce. Among them, lightweight and low - cost batteries have become the first choice in the market. Currently, the best process plan for preparing lightweight and low - cost batteries is full - stamping grid, which can reduce weight, lower cost and improve production efficiency, and the consistency performance of the product is excellent. However, this process has two difficult - to - solve problems. One is that the change in the structure of the stamped positive grid promotes a reduction in the contact area between the grid and the lead paste. The current generated on the surface area of about 500m 2 of the lead paste surface must be concentrated on the surface of the grid of about 40cm 2 ; the other is that the surface of the grid is too uniform and smooth, resulting in poor bonding performance between the grid and the lead paste. The existence of the above two problems leads to a multiple increase in the interfacial resistance, seriously limiting the capacity and life of the electrode plate.

[0003] To address the problem of the reduced contact area between the grid and the lead paste, it is necessary to prepare an improved interface with high conductivity to improve the electrical contact between the active material and the grid. In the prior art, replacing the Pb - Ca grid alloy with a Pb - Sb alloy is the main solution, but the high - Sb alloy grid will cause the problem of water decomposition, and the low - Sb alloy grid is difficult to stamp due to the problem of thermal cracking. To address the problem of the overly uniform and smooth surface of the grid, the rate of the discharge process in the entire large area is the same, which easily leads to the accumulation of PbSO4 crystals into large clusters. Therefore, to prevent the formation of these large clusters of PbSO4 crystals, the surface of the grid should be rough.

[0004] Electroplating a lower content of Sb and Sn onto the surface of the Pb - Ca alloy grid can solve the problem of difficult stamping of the low - antimony alloy grid, increase the corrosion resistance of the grid, and achieve roughening of the stamping grid surface, thus solving the above two problems. Therefore, realizing the electroplating of a lower content of Sb and Sn onto the surface of the Pb - Ca alloy grid through simple process operations is of great significance for extending the service life of lead - acid batteries. Summary of the Invention

[0005] The purpose of the present invention is to provide a preparation method of a long - life lightweight lead - acid battery, which is simple and can extend the service life of lead - acid batteries.

[0006] The purpose of the present invention can be achieved by the following technical solutions:

[0007] A long - life lightweight lead - acid battery, wherein the positive electrode plate of the lead - acid battery is prepared by coating a positive lead paste containing stannous sulfate and antimony trioxide on a Pb - Ca - Sn - Al stamping grid.

[0008] There are two structures in the corrosion layer at the interface between the lead-acid battery grid and PAM (positive active material): a dense inner layer fixed on the grid metal and a porous outer layer in contact with the electrolyte and the PAM skeleton. Both the PAM and the corrosion layer consist of a crystalline region and a gel region. The presence of the gel region forms a dynamic structural element in the electrode plate, which is composed of hydrated linear polymer chains and can respond to the volume expansion and contraction that occur in the structures of the PAM and the corrosion layer during the charge-discharge cycle. This characteristic reduces the tendency of the structure to disintegrate. Therefore, when the outer condensed structure is better, the inner corrosion layer will not break, and it only contains PbO or PbO n (n≥1.5), and PbSO4 is not formed. In the outer layer, the gel region connects the crystalline regions and generates electron and proton conductivity by relying on the polymer chains. The resistance of the gel region depends on the concentration of the polymer chains in the gel and their connections. The PAM density has the greatest influence on the resistance of the gel region because as the gel density increases, the distance between the polymer chains will shorten, but this will inevitably increase the amount of lead paste, which runs counter to the characteristics of being lightweight and low-cost. Introducing dopants such as Sb and Sn into the gel region can play a role in improving the interfacial conductivity.

[0009] Before formation, the lead-acid battery is first subjected to reverse charging to electroplate Sb and Sn in the lead paste onto the surface of the positive electrode grid, and then internal formation is completed, and it is activated by high-current charging after discharging;

[0010] The current for the high-current charging is 1 - 1.5C.

[0011] Furthermore, the positive electrode lead paste includes 0.05 - 0.25 wt% of stannous sulfate and 0.05 - 0.25 wt% of antimony trioxide.

[0012] Furthermore, the preparation steps of the lead-acid battery are as follows:

[0013] Step 1: Use a Pb-Ca-Sn-Al alloy to stamping and form the positive electrode grid;

[0014] Step 2: Prepare the positive electrode lead paste, coat the positive electrode lead paste on the positive electrode grid, and perform a curing treatment to form a corrosion layer interface to obtain a positive electrode plate;

[0015] Step 3: After cutting the cured positive electrode plate, assemble it into a lead-acid battery, and perform reverse charging to electroplate part of Sb and Sn in the lead paste onto the surface of the grid, so that the grid forms a rough interface containing low antimony-tin;

[0016] Step 4: Subject the reverse-charged lead-acid battery to internal formation, and after normal formation charge and discharge, a polymer gel network containing antimony-tin is formed in the grid interface and the PAM;

[0017] Step 5: Post-discharge after internalization. The product is obtained by charging with a large current to activate it. After discharging, it is further charged and activated with a large current to promote the conversion of more PbO2 at the interface, thereby improving the interface structure.

[0018] In a lead-acid battery, during the charging process, the positive electrode plate undergoes an oxidation reaction to generate PbO. This oxidation product usually adheres to the positive electrode plate in the form of a thin layer and becomes part of the corrosion layer. PbO usually exists in a porous form and has poor conductivity, which makes it the main component of the passivation layer and can slow down further corrosion. However, the low conductivity of PbO will cause an increase in the internal resistance of the battery. Sb and Sn can act as electrocatalysts to promote the further oxidation of PbO to PbO n When PbO is oxidized to PbO n (n < 1.5), the formed oxide has high conductivity. When the stoichiometric coefficient n of PbO n reaches 1.4 - 1.5, their specific conductivity will tend to be the same as that of PbO2. Therefore, the interface of the corrosion layer formed on the electrode will have high conductivity.

[0019] Furthermore, the mass percentages of the respective metal components in the Pb-Ca-Sn-Al alloy are: Ca: 0.06 - 0.10%, Sn: 1.0 - 1.2%, Ag: 0.001 - 0.002%, La: 0 - 0.005%, Al: 0 - 0.01%, and the balance is Pb.

[0020] Even further, the mass percentages of the respective metal components in the Pb-Ca-Sn-Al alloy are: Ca: 0.06%, Sn: 1.2%, Ag: 0.002%, La: 0.005%, Al: 0.01%, and the balance is Pb.

[0021] Furthermore, the curing treatment adopts a high-temperature and high-humidity curing process, with the temperature set at 70 - 80°C and the humidity set at 98 - 99%RH.

[0022] Furthermore, the current density of the reverse charge is set to 5 - 10 mA / cm relative to the positive electrode plate grid 2 .

[0023] Furthermore, the duration of the reverse charge is 20 - 40 min.

[0024] Furthermore, in Step 5, the specific setting of the discharge is: discharging with a discharge current of 10 A until the cut-off voltage of 10.5 V per cell.

[0025] Furthermore, in Step 5, the specific setting of the large-current charging is: charging with a large current limited to 1C - 1.5C. When the voltage reaches 14.7 V, switch to the constant-voltage mode for charging, and stop charging when the charging current reaches 0.03C.

[0026] Through the above method, the batch manufacturing of lightweight and low-cost lead-acid batteries is simply and easily achieved, solving the problems of the interface area and smoothness of the grid lead paste. The perfect interface structure increases the current conduction conductivity between crystals, ensuring a large-capacity output; the corrosion layer and the network gel structure in PAM protect the structural elasticity of the corrosion layer and PAM, showing the long-life characteristic of non-decaying capacity cycle durability.

[0027] The lightweight and long-life lead-acid battery for electric bicycles provided by the present invention has the product characteristics of low cost, light weight, long life, easy production, and maintenance-free, which can not only bring easy profits to enterprises but also bring a more pleasant experience to users.

[0028] The beneficial effects of the present invention:

[0029] (1) For the current process method of electro-depositing Sb and Sn on the surface of the Pb-Ca alloy grid, there is mainly an additional electro-deposition production line after grid stamping and before pasting. This process is relatively complex. In the present invention, during the production of the electrode plate and the formation of the active material, the best Sb-Sn interface structure is formed on the surface of the Pb-Ca alloy grid. Using the reverse charge electrochemical formation process, the positive electrode is transformed into a cathode, and Sb 2+ and Sn 2+ in the positive electrode paste undergo a cathodic electrolytic reduction reaction to generate Sb and Sn metals, thereby electro-depositing Sb and Sn in the positive electrode paste onto the grid surface first, and then performing normal formation. After the formation of the active material is completed, it can be charged with a large current to activate, further improving the interface structure.

[0030] (2) In the present invention, Sb and Sn are doped in the positive electrode paste. On the one hand, Sb and Sn can serve as polymer chain connection points. After introducing antimony and tin ions in the gel area, the polymer chains are interconnected to form a network, and a certain number of gel areas are formed in the outer corrosion layer. The gel areas play a hinge role in absorbing mechanical stress, and the speed of electron transmission is greatly accelerated. On the other hand, the Sb and Sn dopants can affect the sulfidation process of the corrosion layer. In H2SO4, the corrosion layer on the lead-calcium grid starts to sulfide earlier than the corrosion layer formed on the lead-antimony grid.

[0031] (3) During the pasting process, the lead paste containing Sb and Sn is pressed onto the grid surface, and a thick PbO / PbO n corrosion layer is formed on the electrode plate during the curing process; during the formation process, the battery is pre-reversed charged to electro-deposit and dope Sb and Sn into the grid / paste interface, achieving a rough interface of the grid, inhibiting the formation of large lumps of lead sulfate and the role of the electrocatalyst. Sb / Sn acts as a polymer chain connection point, thereby forming an interface structure of a polymer chain network; finally, through charging with a large current, the dissolution of oxygen is promoted, and the supersaturated oxygen at the interface promotes PbO nRapid conversion occurs, forming a large amount of PbO2 on the interface, which intertwines and aggregates. Eventually, more electric bridges are formed between the positive electrode active material and the corrosion layer, improving the interface structure and enabling the positive electrode active material to have a longer discharge time. Description of the Drawings

[0032] The present invention will be further described below in conjunction with the drawings.

[0033] Figure 1 It is a cyclic curve graph of the embodiments and comparative examples of the present invention. Specific Embodiments

[0034] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0035] Embodiment 1

[0036] This embodiment provides a long-life lightweight lead-acid battery. The positive electrode plate of the lead-acid battery is prepared by coating a positive lead paste containing stannous sulfate and antimony trioxide on a Pb-Ca-Sn-Al stamped grid.

[0037] Before formation, the lead-acid battery is pre-charged in reverse to electro-deposit Sb and Sn in the lead paste on the surface of the positive electrode grid.

[0038] The positive lead paste includes 0.1 wt% of stannous sulfate and 0.1 wt% of antimony trioxide.

[0039] The preparation steps of the battery are as follows:

[0040] Step 1: A positive electrode grid is formed by stamping a Pb-Ca-Sn-Al alloy (Ca: 0.06%, Sn: 1.2%, Ag: 0.002%, La: 0.005%, Al: 0.01%, the balance is Pb).

[0041] Step 2: Prepare a positive lead paste. The lead paste contains 10 wt% of water, 8 wt% of sulfuric acid, 5 wt% of red lead, 0.1 wt% of stannous sulfate and 0.1 wt% of antimony trioxide, and the balance is lead powder. The positive lead paste is coated on the positive electrode grid and subjected to a curing treatment. The curing process parameters are set as follows: temperature 75°C, humidity 99% RH, and curing time 24 h to form a corrosion layer interface and obtain a positive electrode plate.

[0042] Step 3: After cutting the cured positive electrode plate, it is assembled into a lead-acid battery and charged in reverse. Using 5 mA / cm relative to the positive electrode grid 2Recharge the battery at a current density of 30 min for 30 minutes;

[0043] Step 4. Subject the recharged lead-acid battery to internal formation;

[0044] Step 5. Discharge the battery after internal formation. During the discharge process, discharge at a discharge current of 10 A until the termination voltage of 10.5 V per cell is reached. After discharge, perform rapid charging with a large current of 1 C. When the voltage reaches 14.7 V, switch to the constant voltage mode for charging, and stop charging when the charging current reaches 0.03 C to obtain the finished product.

[0045] Example 2

[0046] The difference from Example 1 is only that the proportion of stannous sulfate in the positive paste is adjusted to 0.05 wt%.

[0047] This example provides a long-life lightweight lead-acid battery. The positive electrode plate of the lead-acid battery is prepared by coating a positive paste containing stannous sulfate and antimony trioxide on a Pb-Ca-Sn-Al stamped grid;

[0048] Before formation, the lead-acid battery is recharged to electroplate Sb and Sn in the positive paste onto the surface of the positive grid;

[0049] The positive paste includes 0.05 wt% of stannous sulfate and 0.1 wt% of antimony trioxide.

[0050] The preparation steps of the battery are as follows:

[0051] Step 1. Use a Pb-Ca-Sn-Al alloy (Ca: 0.06%, Sn: 1.2%, Ag: 0.002%, La: 0.005%, Al: 0.01%, the balance is Pb) to stamp and form the positive grid;

[0052] Step 2. Prepare the positive paste. The paste contains 10 wt% water, 8 wt% sulfuric acid, 5 wt% red lead, 0.05 wt% of stannous sulfate and 0.1 wt% of antimony trioxide, and the balance is lead powder. Coat the positive paste on the positive grid and perform a curing treatment. The curing process parameters are set as follows: temperature 75°C, humidity 99% RH, curing time 24 h, to form a corrosion layer interface and obtain the positive electrode plate;

[0053] Step 3. After cutting the cured positive electrode plate, assemble it into a lead-acid battery and perform reverse charging. Use a current density of 5 mA / cm relative to the positive grid 2 Recharge the battery for 30 minutes;

[0054] Step 4. Subject the recharged lead-acid battery to internal formation;

[0055] Step 5: Post-discharge after internal formation. During the discharge process, discharge with a discharge current of 10 A until the cut-off voltage of 10.5 V per cell is reached. After discharge, perform rapid charging with a large current of 1 C. When the voltage reaches 14.7 V, switch to the constant voltage mode for charging, and stop charging when the charging current reaches 0.03 C to obtain the finished product.

[0056] Example 3

[0057] The difference from Example 1 is only that the proportion of stannous sulfate in the positive paste is adjusted to 0.25 wt%.

[0058] This example provides a long-life lightweight lead-acid battery. The positive electrode plate of the lead-acid battery is prepared by coating a Pb-Ca-Sn-Al stamped grid with a positive paste containing stannous sulfate and antimony trioxide.

[0059] Before internal formation, the lead-acid battery is pre-charged reversely to electroplate Sb and Sn in the paste onto the surface of the positive grid.

[0060] The positive paste includes 0.25 wt% of stannous sulfate and 0.1 wt% of antimony trioxide.

[0061] The preparation steps of the battery are as follows:

[0062] Step 1: Use a Pb-Ca-Sn-Al alloy (Ca: 0.06%, Sn: 1.2%, Ag: 0.002%, La: 0.005%, Al: 0.01%, the balance is Pb) to stamp and form the positive grid.

[0063] Step 2: Prepare the positive paste. The paste contains 10 wt% water, 8 wt% sulfuric acid, 5 wt% red lead, 0.25 wt% of stannous sulfate and 0.1 wt% of antimony trioxide, and the balance is lead powder. Coat the positive paste on the positive grid and perform curing treatment. The curing process parameters are set as: temperature 75°C, humidity 99% RH, curing time 24 h, to form a corrosion layer interface and obtain the positive electrode plate.

[0064] Step 3: After cutting the cured positive electrode plate, assemble it into a lead-acid battery and perform reverse charging. Use a current density of 5 mA / cm 2 relative to the positive grid to perform reverse charging of the battery for 30 min.

[0065] Step 4: Perform internal formation on the reversely charged lead-acid battery.

[0066] Step 5: Post-discharge after internal formation. During the discharge process, discharge with a discharge current of 10 A until the cut-off voltage of 10.5 V per cell is reached. After discharge, perform rapid charging with a large current of 1 C. When the voltage reaches 14.7 V, switch to the constant voltage mode for charging, and stop charging when the charging current reaches 0.03 C to obtain the finished product.

[0067] Example 4

[0068] The difference from Example 1 is only that the proportion of antimony trioxide in the positive electrode lead paste is adjusted to 0.05 wt%.

[0069] This example provides a long-life lightweight lead-acid battery. The positive electrode plate of the lead-acid battery is prepared by coating a positive electrode lead paste containing stannous sulfate and antimony trioxide on a Pb-Ca-Sn-Al stamping grid;

[0070] Before formation, the lead-acid battery is pre-charged in reverse to electroplate Sb and Sn in the lead paste onto the surface of the positive electrode grid;

[0071] The positive electrode lead paste includes 0.1 wt% of stannous sulfate and 0.05 wt% of antimony trioxide.

[0072] The preparation steps of the battery are as follows:

[0073] Step 1: A positive electrode grid is formed by stamping a Pb-Ca-Sn-Al alloy (Ca: 0.06%, Sn: 1.2%, Ag: 0.002%, La: 0.005%, Al: 0.01%, the balance is Pb);

[0074] Step 2: Prepare a positive electrode lead paste. The lead paste contains 10 wt% water, 8 wt% sulfuric acid, 5 wt% red lead, 0.1 wt% of stannous sulfate and 0.05 wt% of antimony trioxide, and the balance is lead powder. Coat the positive electrode lead paste on the positive electrode grid and perform a curing treatment. The curing process parameters are set as follows: temperature 75°C, humidity 99% RH, curing time 24 h, to form a corrosion layer interface and obtain a positive electrode plate;

[0075] Step 3: After cutting the cured positive electrode plate, assemble it into a lead-acid battery and perform reverse charging. The battery is reversely charged for 30 min at a current density of 5 mA / cm 2 relative to the positive electrode grid;

[0076] Step 4: Subject the reversely charged lead-acid battery to internal formation;

[0077] Step 5: Discharge after internal formation. During the discharge process, discharge at a discharge current of 10 A until the termination voltage of 10.5 V per cell is reached. After discharge, perform rapid charging with a large current of 1C. When the voltage reaches 14.7 V, switch to the constant voltage mode for charging, and stop charging when the charging current reaches 0.03C to obtain the finished product.

[0078] Example 5

[0079] The difference from Example 1 is only that the proportion of antimony trioxide in the positive electrode lead paste is adjusted to 0.25 wt%.

[0080] This embodiment provides a long-life lightweight lead-acid battery. The positive electrode plate of the lead-acid battery is prepared by coating a Pb-Ca-Sn-Al stamping grid with a positive electrode lead paste containing stannous sulfate and antimony trioxide.

[0081] Before formation, the lead-acid battery is reverse charged to electroplate Sb and Sn in the lead paste onto the surface of the positive electrode grid.

[0082] The positive electrode lead paste includes 0.1 wt% of stannous sulfate and 0.25 wt% of antimony trioxide.

[0083] The preparation steps of the battery are as follows:

[0084] Step 1: Use a Pb-Ca-Sn-Al alloy (Ca: 0.06%, Sn: 1.2%, Ag: 0.002%, La: 0.005%, Al: 0.01%, the balance is Pb) to stamp and form the positive electrode grid.

[0085] Step 2: Prepare the positive electrode lead paste. The lead paste contains 10 wt% water, 8 wt% sulfuric acid, 5 wt% red lead, 0.1 wt% of stannous sulfate and 0.25 wt% of antimony trioxide, and the balance is lead powder. Coat the positive electrode lead paste on the positive electrode grid and perform a curing treatment. The curing process parameters are set as follows: temperature 75°C, humidity 99% RH, curing time 24 h, to form a corrosion layer interface and obtain the positive electrode plate.

[0086] Step 3: After cutting the cured positive electrode plate, assemble it into a lead-acid battery and perform reverse charging. Use a current density of 5 mA / cm relative to the positive electrode grid 2 to reverse charge the battery for 30 min.

[0087] Step 4: Perform internal formation on the reverse-charged lead-acid battery.

[0088] Step 5: Discharge after internal formation. During the discharge process, discharge with a 10 A discharge current until the cut-off voltage of 10.5 V per cell is reached. After discharge, perform rapid charging with a large current of 1C. When the voltage reaches 14.7 V, switch to the constant voltage mode for charging, and stop charging when the charging current reaches 0.03C to obtain the finished product.

[0089] Example 6

[0090] The difference from Example 1 is only that the reverse charging current density is adjusted to 1 mA / cm 2 and the reverse charging time is adjusted to 10 min.

[0091] This embodiment provides a long-life lightweight lead-acid battery. The positive electrode plate of the lead-acid battery is prepared by coating a Pb-Ca-Sn-Al stamping grid with a positive electrode lead paste containing stannous sulfate and antimony trioxide.

[0092] Before formation, the lead-acid battery is pre-charged in reverse to electro-deposit Sb and Sn in the lead paste onto the surface of the positive grid;

[0093] The positive lead paste contains 0.1 wt% stannous sulfate and 0.1 wt% antimony trioxide.

[0094] The steps for preparing the battery are as follows:

[0095] Step 1: A positive grid is obtained by stamping a Pb-Ca-Sn-Al alloy (Ca: 0.06%, Sn: 1.2%, Ag: 0.002%, La: 0.005%, Al: 0.01%, the balance is Pb);

[0096] Step 2: Prepare a positive lead paste, which contains 10 wt% water, 8 wt% sulfuric acid, 5 wt% red lead, 0.1 wt% stannous sulfate and 0.1 wt% antimony trioxide, and the balance is lead powder. Coat the positive lead paste on the positive grid and perform a curing treatment. The curing process parameters are set as: temperature 75°C, humidity 99% RH, and curing time 24 h to form a corrosion layer interface, obtaining a positive electrode plate;

[0097] Step 3: After cutting the cured positive electrode plate, assemble it into a lead-acid battery and perform reverse charging. Use a current density of 1 mA / cm 2 relative to the positive grid to perform reverse charging of the battery for 10 min;

[0098] Step 4: Perform in-situ formation on the lead-acid battery after reverse charging;

[0099] Step 5: Discharge after in-situ formation. During the discharge process, discharge with a discharge current of 10 A until the cut-off voltage of 10.5 V per cell. After discharge, perform rapid charging with a large current of 1C. When the voltage reaches 14.7 V, switch to the constant voltage mode for charging, and stop charging when the charging current reaches 0.03C to obtain the finished product.

[0100] Example 7

[0101] The difference from Example 1 is only that the reverse charging current density is adjusted to 20 mA / cm 2 and the reverse charging time is adjusted to 60 min.

[0102] This example provides a long-life lightweight lead-acid battery. The positive electrode plate of the lead-acid battery is prepared by coating a positive lead paste containing stannous sulfate and antimony trioxide on a Pb-Ca-Sn-Al stamping grid;

[0103] Before formation, the lead-acid battery is pre-charged in reverse to electro-deposit Sb and Sn in the lead paste onto the surface of the positive grid;

[0104] The positive paste includes 0.1 wt% stannous sulfate and 0.1 wt% antimony trioxide.

[0105] The preparation steps of the battery are as follows:

[0106] Step 1: Use a Pb-Ca-Sn-Al alloy (Ca: 0.06%, Sn: 1.2%, Ag: 0.002%, La: 0.005%, Al: 0.01%, the balance is Pb) to stamp and form a positive grid.

[0107] Step 2: Prepare a positive paste. The paste contains 10 wt% water, 8 wt% sulfuric acid, 5 wt% red lead, 0.1 wt% stannous sulfate and 0.1 wt% antimony trioxide, and the balance is lead powder. Coat the positive paste on the positive grid and perform a curing treatment. The curing process parameters are set as: temperature 75°C, humidity 99% RH, and curing time 24 h to form a corrosion layer interface and obtain a positive plate.

[0108] Step 3: After cutting the cured positive plate, assemble it into a lead-acid battery and perform reverse charging. Use a current density of 20 mA / cm 2 relative to the positive grid to perform reverse charging of the battery for 60 min.

[0109] Step 4: Perform internal formation on the reverse-charged lead-acid battery.

[0110] Step 5: Discharge after internal formation. During the discharging process, discharge with a discharging current of 10 A until the termination voltage of 10.5 V per cell. After discharging, perform rapid charging with a large current of 1C. When the voltage reaches 14.7 V, switch to the constant voltage mode for charging, and stop charging when the charging current reaches 0.03C to obtain the finished product.

[0111] Comparative Example 1

[0112] The difference from Example 1 is that the lead-acid battery does not perform reverse charging before formation and large-current charging after internal formation.

[0113] This comparative example provides a lead-acid battery. The positive plate of the lead-acid battery is prepared by coating a positive paste containing stannous sulfate and antimony trioxide on a Pb-Ca-Sn-Al stamped grid.

[0114] The positive paste includes 0.1 wt% stannous sulfate and 0.1 wt% antimony trioxide.

[0115] The preparation steps of the battery are as follows:

[0116] Step 1: Use a Pb-Ca-Sn-Al alloy (Ca: 0.06%, Sn: 1.2%, Ag: 0.002%, La: 0.005%, Al: 0.01%, the balance is Pb) to stamp and form a positive grid.

[0117] Step 2: Prepare the positive electrode lead paste. The lead paste contains 10 wt% water, 8 wt% sulfuric acid, 5 wt% red lead, 0.1 wt% stannous sulfate, and 0.1 wt% antimony trioxide, with the balance being lead powder. Coat the positive electrode lead paste on the positive electrode grid and perform a curing treatment. The curing process parameters are set as follows: temperature 75°C, humidity 99% RH, and curing time 24 h to form a corrosion layer interface, obtaining the positive electrode plate.

[0118] Step 3: After cutting the cured positive electrode plates, assemble them into a lead-acid battery.

[0119] Step 4: Subject the assembled lead-acid battery to internal formation to obtain the finished product.

[0120] Comparative Example 2

[0121] The difference from Example 1 is that Sn is not added to the positive electrode lead paste of the lead-acid battery.

[0122] This comparative example provides a lead-acid battery. The positive electrode plate of the lead-acid battery is prepared by coating a positive electrode lead paste containing antimony trioxide on a Pb-Ca-Sn-Al stamping grid.

[0123] Before formation, the lead-acid battery is subjected to reverse charging to electrochemically deposit Sb in the lead paste onto the surface of the positive electrode grid.

[0124] The proportion of antimony trioxide in the positive electrode lead paste is 0.1 wt%.

[0125] The preparation steps of the battery are as follows:

[0126] Step 1: Use a Pb-Ca-Sn-Al alloy (Ca: 0.06%, Sn: 1.2%, Ag: 0.002%, La: 0.005%, Al: 0.01%, with the balance being Pb) to stamp and form the positive electrode grid.

[0127] Step 2: Prepare the positive electrode lead paste. The lead paste contains 10 wt% water, 8 wt% sulfuric acid, 5 wt% red lead, and 0.1 wt% antimony trioxide, with the balance being lead powder. Coat the positive electrode lead paste on the positive electrode grid and perform a curing treatment. The curing process parameters are set as follows: temperature 75°C, humidity 99% RH, and curing time 24 h to form a corrosion layer interface, obtaining the positive electrode plate.

[0128] Step 3: After cutting the cured positive electrode plates, assemble them into a lead-acid battery and perform reverse charging. Use a current density of 5 mA / cm 2 relative to the positive electrode grid to perform reverse charging on the battery for 30 min.

[0129] Step 4: Subject the reverse-charged lead-acid battery to internal formation.

[0130] Step 5: Post-discharge after internalization. During the discharge process, discharge with a discharge current of 10 A until the cut-off voltage of 10.5 V per cell is reached. After discharge, perform rapid charging with a large current of 1C. When the voltage reaches 14.7 V, switch to the constant voltage mode for charging, and stop charging when the charging current reaches 0.03C to obtain the finished product.

[0131] The lead-acid batteries produced in Examples 1 - 7 and Comparative Examples 1 - 2 were subjected to cycle verification. Discharge at 10 A until 52.5 V, and charge at constant current and constant voltage (10 A, 73.5 V) for 4 h. The cycle curves of Examples 1 - 7 and Comparative Examples 1 - 2 are shown in the appendix Figure 1 。

[0132] As can be seen from the appendix Figure 1 The fully stamped lead-acid battery produced in Example 1 shows the characteristics of high capacity and slow attenuation compared to Comparative Example 1. Under the guidance of a series of technologies and operations such as grid production, high-temperature curing, and special internalization, an excellent interface structure is formed at the grid interface in Example 1. The high conductivity improves the battery capacity, and the perfect gel network interface extends the grid / PAM electrical contact time and the trend of PAM structure collapse, thus achieving the successful transformation of the fully stamped technology to the long-life lightweight lead-acid battery technology. In Examples 6 and 7, the reverse charge current and time were adjusted. If the reverse charge current and time are insufficient, the cathodic electrolytic reduction reaction of Sb 2+ and Sn 2+ in the positive lead paste is not sufficient, the metal content of Sb and Sn electroplated on the grid interface is low, the capacity is low, and it is not easy to form a uniform and dense alloy layer, and the structure is thin. If the reverse charge current is too large and the time is too long, Sb 2+ and Sn 2+ undergo cathodic electrolytic reduction reaction, and at the same time, Pb 2 + in the positive lead paste is reduced to generate more free lead. The volume of the excessive free lead changes significantly during the subsequent internalization process of converting into active substances, the structure of the positive lead paste is poor, and the lifespan is shortened. And from the results of Comparative Example 2, the roles of Sn and Sb in forming the gel polymer structure are similar, and adding tin to the surface of the lead-calcium grid improves the grid interface conductivity and increases the grid corrosion resistance. The co-deposition potentials of Sb and Sn are similar, and the co-deposition effect is better at the lead-calcium grid interface.

[0133] It should be noted that in this text, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "comprising", "including" or any other variation thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device comprising a series of elements not only includes those elements, but also includes other elements not expressly listed, or further includes elements inherent to such process, method, article or device.

[0134] Although the embodiments of the present invention have been shown and described, those of ordinary skill in the art can understand that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A long-life lightweight lead-acid battery, characterized in that, The positive electrode plate of the lead-acid battery is prepared by coating a Pb-Ca-Sn-Al stamping grid with a positive electrode lead paste containing stannous sulfate and antimony trioxide. Before formation, the lead-acid battery is first reverse charged to electroplate Sb and Sn in the lead paste onto the surface of the positive electrode grid, and then internal formation is completed, followed by activation through high-current charging after discharge. The current for the high-current charging is 1 - 1.5C.

2. A long-life lightweight lead-acid battery according to claim 1, characterized in that The positive electrode lead paste contains 0.05 - 0.25 wt% of stannous sulfate and 0.05 - 0.25 wt% of antimony trioxide.

3. A long-life lightweight lead-acid battery according to claim 1, characterized in that, The preparation steps of the lead-acid battery are as follows: Step 1: A positive electrode grid is formed by stamping a Pb-Ca-Sn-Al alloy. Step 2: A positive electrode lead paste is prepared and coated on the positive electrode grid, followed by curing treatment to form a corrosion layer interface, resulting in a positive electrode plate. Step 3: The cured positive electrode plates are cut and assembled into a lead-acid battery, and reverse charging is carried out to electroplate part of Sb and Sn in the lead paste onto the grid surface. Step 4: The lead-acid battery after reverse charging is subjected to internal formation. Step 5: After internal formation, discharge is carried out, and high-current charging is used for activation to obtain the finished product.

4. A long-life lightweight lead-acid battery according to claim 3, characterized in that, In the Pb-Ca-Sn-Al alloy, the mass percentages of each metal component are: Ca: 0.06 - 0.10%, Sn: 1.0 - 1.2%, Ag: 0.001 - 0.002%, La: 0 - 0.005%, Al: 0 - 0.01%, and the balance is Pb.

5. A long-life lightweight lead-acid battery according to claim 3, characterized in that, In the Pb-Ca-Sn-Al alloy, the mass percentages of each metal component are: Ca: 0.06%, Sn: 1.2%, Ag: 0.002%, La: 0.005%, Al: 0.01%, and the balance is Pb.

6. A long-life lightweight lead-acid battery according to claim 3, characterized in that, The curing treatment uses a high-temperature and high-humidity curing process, with the temperature set at 70 - 80°C and the humidity set at 98 - 99% RH.

7. A long-life lightweight lead-acid battery according to claim 3, characterized in that, The current density of the reverse charge is set to be 5-10 mA / cm relative to the positive plate grid 2 .

8. A long-life lightweight lead-acid battery according to claim 3, characterized in that, The duration of the reverse charging is 20 - 40 min.

9. A long-life lightweight lead-acid battery according to claim 3, characterized in that, In Step 5, the specific setting for the discharge is: discharging with a 10A discharge current until the termination voltage of 10.5V per cell is reached.

10. A long-life lightweight lead-acid battery according to claim 3, characterized in that, In Step 5, the specific setting for the high-current charging is: charging with a limited current of 1C - 1.5C high current. When the voltage reaches 14.7V, switch to the constant voltage mode for charging, and stop charging when the charging current reaches 0.03C.

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