Manufacturing process of flooded auxiliary battery with high charge acceptance performance and flooded auxiliary battery

Abstract

The invention provides a manufacturing process of a flooded auxiliary battery with high charge acceptance performance and the flooded auxiliary battery. A formula for preparing positive plate lead plaster comprises the following components in parts by weight: 100 parts of lead powder, 5-9 parts of dilute sulphuric acid, 9-13 parts of deionized water, 0.06-0.12 part of antimony trioxide, 0.2-0.6 part of a sodium peroxide pro-oxidant and 0.06-0.12 part of ultra-short fibers; a negative plate lead paste formula in the preparation of the negative electrode lead paste comprises the following components in parts by weight: 100 parts of lead powder, 6-11 parts of dilute sulfuric acid, 8-13 parts of deionized water, 0.06-0.10 part of ultra-short fibers, 0.2-0.4 part of an LN-01 composite additive, 0.5-1.1 parts of superfine barium sulfate and 0.1-0.3 part of Norway lignin; 10%-20% of a high-conductivity composite electrolyte additive is added into a dilute sulfuric acid electrolyte in the primary acid adding process of battery formation. The flooded auxiliary battery produced by adopting the manufacturing process is good in low-voltage and deep-discharge charging acceptance performance, and meets the working condition requirements of deep-discharge and rapid recharging of new energy automobiles.

Description

Technical Field

[0001] The invention relates to a manufacturing process of a liquid-rich auxiliary battery. Background Art

[0002] With the development of new energy vehicles, traditional cars are integrated with the Internet and artificial intelligence. Smart cars are no longer a means of transportation in the traditional sense, but have evolved into a service system and ecosystem platform. Intelligent driving technologies such as automatic parking, automatic driving, and vehicle autonomous judgment have greatly improved driving safety and comfort, bringing users a better driving experience; intelligent car networking technology connects cars and the Internet to achieve remote control, intelligent navigation, voice interaction, online entertainment and other services, bringing users a more intelligent car experience.

[0003] With the continuous upgrading of new energy vehicles, in addition to the conventional power demand, the 12V low-voltage auxiliary battery also needs to meet the new functional requirements brought by intelligence, safety and autonomous driving, such as remote monitoring power supply, OTA upgrade power supply, low-voltage battery also needs to assist braking and steering, when the main battery fails, the low-voltage battery needs to meet the safety energy supply, auxiliary safety driving function, driving and parking prediction, dynamic voltage stabilization, etc. High intelligence, in-vehicle Internet technology, and safe autonomous driving technology are the inevitable trends in the future development of new energy vehicles, and higher requirements are also put forward for low-voltage auxiliary batteries.

[0004] New energy vehicle application conditions and current problems:

[0005] 1. Low DC-DC conversion charging voltage: Considering the range of new energy vehicles, some OEMs will reduce the charging voltage of DCDC conversion. At the same time, in addition to operating vehicles, EV new energy vehicles are mainly used for short-term driving in the city, with short charging time, and the auxiliary battery is undercharged for a long time, resulting in power loss;

[0006] 2. High power consumption and slow charging recovery: New energy vehicles have high dark current and electrical appliances that consume a lot of power. Conventional low-voltage batteries have poor deep discharge charging recovery and require a long charging time. This affects the service life of low-voltage batteries and consumes more high-voltage electricity, affecting the range.

[0007] Therefore, new energy vehicles have higher requirements on the low-voltage charging acceptance performance and deep discharge charging recovery performance of auxiliary batteries, and it is urgent to carry out applicability development to meet the development needs of new energy vehicles. Summary of the invention

[0008] Based on the above background, the present invention provides a manufacturing process for a flooded auxiliary battery with high charge acceptance performance to solve the problem of poor low-voltage and deep-discharge charge acceptance performance of existing flooded batteries.

[0009] The technical solution of the present invention is: a manufacturing process of a flooded auxiliary battery with high charge acceptance performance, characterized in that it includes the following steps:

[0010] Preparation of positive electrode lead paste:

[0011] The positive electrode lead paste formula comprises the following components in parts by weight:

[0012]

[0013] The oxygen promoter is used to release oxygen during the plate curing process to form an oxidized corrosion layer at the grid interface;

[0014] Preparation of negative electrode lead paste:

[0015] The negative electrode lead paste formula comprises the following components in parts by weight:

[0016]

[0017] Plate preparation: The lead paste is transferred to the paste coating hopper and evenly coated on the surface of the grid belt by the paste coating machine, and then the grid belt is cut to produce a single wet plate. The single wet plate is quickly dried in a drying kiln and then transferred to a curing and drying chamber, and cured and dried into a dry raw plate through a curing and drying process;

[0018] Pole group encapsulation: The negative electrode is encapsulated with a separator;

[0019] Battery assembly: Immerse the ends of the encapsulated and assembled pole group ears into a mold filled with molten lead, quickly cast and weld the positive and negative plate ears in parallel, then load the welded pole group into the battery tank, weld the adjacent connectors together, distribute them into each cell of the battery tank, use the butt welding process to butt weld the pole group, and then heat seal the large cover;

[0020] Battery formation: A dilute sulfuric acid solution is used for primary acid addition, and 10% to 20% of a high-conductivity composite electrolyte additive is added to the dilute sulfuric acid electrolyte for primary acid addition. The composition and weight ratio of the high-conductivity composite electrolyte additive are lithium sulfate: aluminum sulfate: germanium sulfate: silicon dioxide: pure water = (1±0.1): (3±0.2): (2±0.2): (5±0.3): (8±0.5). An intermittent constant current charging formation process is used for charging formation. After the formation is completed, a non-reversing acid process is used. Only a small amount of acid is added to each cell of the battery tank for a second time to adjust the liquid level, and at the same time, the electrolyte mixed acid density is ensured to be 1.280±0.005g / cm 3 .

[0021] The paste making process of the positive electrode lead paste is as follows:

[0022] 1) Weigh the raw materials according to the weight of the positive electrode formula; dry-mix sodium peroxide, antimony trioxide, ultra-short fibers and lead powder, add deionized water accounting for 25-35% of the total mass of deionized water, control the water addition time to 1-2 minutes, and stir for 2-4 minutes;

[0023] 2) Add the remaining deionized water, control the water addition time to 3-4 minutes, and continue stirring for 3-6 minutes;

[0024] 3) Then add 1.38g / cm 3 For dilute sulfuric acid solution, the acid addition time should be controlled within 7 to 10 minutes;

[0025] 4) Finally, open the cooling system, continue stirring, and cool down to 50±3°C to obtain the positive electrode lead paste.

[0026] 3. The manufacturing process of the flooded auxiliary battery with high charge acceptance performance according to claim 1 is characterized in that the negative electrode lead paste is prepared by:

[0027] 1) Weigh the raw materials according to the weight of the negative electrode formula; stir and mix the LN-01 composite additive, ultrafine barium sulfate, Norwegian lignin, ultrashort fibers and lead powder, add deionized water accounting for 25-35% of the total mass of deionized water, control the addition time to 1.5-2.5 minutes, and stir for 2-4 minutes;

[0028] 2) Add the remaining deionized water, control the water addition time to 3-4 minutes, and continue stirring for 5-10 minutes;

[0029] 3) Then add 1.38g / cm 3 For dilute sulfuric acid solution, the acid addition time should be controlled within 7 to 10 minutes;

[0030] 4) Finally, open the cooling system, continue stirring, and cool down to 50±3℃ to obtain the negative electrode lead paste.

[0031] The oxygen promoter is sodium peroxide, and the crystal size of sodium peroxide is 1.5-4 μm. The sodium peroxide crystal releases oxygen during the plate curing process, which helps to form an oxidized corrosion layer at the grid interface, reduces the grid interface resistance, and improves the charging acceptance.

[0032] The LN-01 composite additive is a composite crystal obtained by ball milling lead sulfate crystals and activated carbon in a weight ratio of (1±0.2):(1±0.2). The particle size of the composite crystal is 1.5-4.5 μm.

[0033] The separator is a PE separator.

[0034] The preparation method of the high-conductivity composite electrolyte additive is as follows: weigh the corresponding raw materials according to the following weight ratio: lithium sulfate: aluminum sulfate: germanium sulfate: silicon dioxide: pure water = (1±0.1): (3±0.2): (2±0.2): (5±0.3): (8±0.5), add lithium sulfate, aluminum sulfate, germanium sulfate and silicon dioxide into pure water according to the above ratio, and shear them with a high-speed shearing machine at room temperature. The high-speed shearing process parameters are 4000-6000rpm, 20-40min, and the preparation of the high-conductivity composite electrolyte additive is completed; the composite electrolyte additive improves the degree of acid stratification under deep discharge conditions of the battery, and at the same time increases the activity of the electrolyte in a low temperature environment, thereby improving the charging acceptance performance.

[0035] The battery formation process also includes heat sealing of the small cover after adjusting the liquid level, air tightness testing, and finally high current testing and battery cleaning and drying.

[0036] The specific method of welding adjacent connectors together in the battery assembly is as follows: applying a high current to the connectors of the positive and negative electrode groups through a through-wall welding machine fixture to partially melt the connectors and maintain pressure for 3-5 seconds.

[0037] Another aspect of the present invention provides a flooded auxiliary battery prepared by using the above-mentioned manufacturing process of a flooded auxiliary battery with high charge acceptance performance.

[0038] The beneficial effects of the present invention are as follows: the present invention adds LN-01 composite additive (a composite crystal obtained by ball-milling lead sulfate crystals and activated carbon according to (1±0.2):(1±0.2)) into the negative electrode lead paste, the PbSO4 component in the crystal increases the pore size of the negative electrode, provides an enhanced ion transmission channel, and improves the rate performance of the negative electrode active material. At the same time, the lead-containing substance is used to modify the carbon material, thereby improving the affinity of the additive and the negative electrode active material, solving the poor contact problem caused by the large density difference between lead and carbon materials, and improving the negative electrode charging recovery performance; adding 10% to 20% of the high-conductivity composite electrolyte additive to the dilute sulfuric acid electrolyte in the battery formation acid charging process improves the degree of acid stratification under the deep discharge condition of the battery, and at the same time improves the activity of the electrolyte in a low temperature environment, thereby improving the charging acceptance performance; the battery produced by the manufacturing process and the positive and negative electrode lead paste formula provided by the present invention has good low-voltage and deep discharge charging acceptance performance, has the characteristics of ultra-high charging acceptance performance, meets the working condition requirements of deep discharge and rapid recharging of new energy vehicles, and meets the use requirements of pure electric new energy vehicles. DETAILED DESCRIPTION

[0039] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and is by no means intended to limit the present invention and its application or use. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without carrying out creative work are within the scope of protection of the present invention.

[0040] Technologies, methods, and apparatus known to ordinary technicians in the relevant field may not be discussed in detail, but where appropriate, such technologies, methods, and apparatus should be considered part of the authorization specification.

[0041] Example 1

[0042] A formula for a high charge acceptance-rich auxiliary battery plate and an auxiliary battery manufacturing process, wherein the positive lead paste formula comprises the following components in parts by weight:

[0043]

[0044] The positive electrode and paste process is:

[0045] 1) Dry-mix antimony trioxide, ultra-short fibers and lead powder, add deionized water accounting for 25% of the total mass of deionized water, control the water addition time to 1.5 minutes, and stir for 3 minutes;

[0046] 2) Add the remaining deionized water for 3 minutes and continue stirring for 4 minutes;

[0047] 3) Then add 1.38g / cm 3 Dilute sulfuric acid solution, the acid addition time is controlled within 8 minutes;

[0048] 4) Finally, open the cooling system, continue stirring, and cool down to 50°C to obtain the positive electrode lead paste;

[0049] The negative electrode lead paste formula contains the following components in parts by weight:

[0050]

[0051]

[0052] The negative electrode and paste process is:

[0053] 1) First, mix the ultrafine barium sulfate, Norwegian lignin, ultrashort fibers and lead powder, add deionized water accounting for 25% of the total mass of deionized water, add for 2 minutes, and stir for 3 minutes;

[0054] 2) Add the remaining deionized water for 3 minutes and continue stirring for 6 minutes;

[0055] 3) Then add 1.38g / cm 3 Dilute sulfuric acid solution, the acid addition time is controlled within 8 minutes;

[0056] 4) Finally, open the cooling system, continue stirring, and cool down to 50°C to obtain the negative electrode lead paste.

[0057] The lead paste is transferred to the paste coating hopper and evenly coated on the surface of the grid strip by the paste coating machine, and then the grid strip is cut to produce a single wet plate. The single wet plate is quickly dried in a drying kiln and then transferred to a curing drying chamber, and cured and dried into a dry raw plate through a curing and drying process;

[0058] The pole group encapsulation uses PE separator to encapsulate the negative electrode;

[0059] The battery is assembled using a COS casting welding machine. The ends of the encapsulated and assembled pole group ears are immersed in a mold filled with molten lead. The positive and negative plate ears are quickly cast and welded in parallel. The welded pole groups are then loaded into the battery tank. A high current is applied to the connectors of the positive and negative pole groups through the through-wall welding machine fixture to partially melt the connectors. The pressure is maintained for 3 seconds, and the adjacent connectors are welded together and distributed into each single cell of the battery tank. The pole groups are butt-welded using a butt welding process, and then the large cover is heat-sealed.

[0060] Battery formation: A dilute sulfuric acid solution is used for primary acid addition. 10% of a highly conductive composite electrolyte additive is added to the dilute sulfuric acid electrolyte for primary acid addition. The composition and weight ratio of the composite electrolyte additive are (lithium sulfate: aluminum sulfate: germanium sulfate: silicon dioxide: pure water = 0.95: 2.95: 2: 5.1: 8.1). An intermittent constant current charging formation process is used for charging formation. After the formation, a non-reversing acid process is used. Only each cell of the battery tank is acidified for a second time. The liquid level is adjusted. The final electrolyte mixed acid density is 1.280 g / cm 3 , finally, heat seal the small cover, perform air tightness test, and finally perform high current test and battery cleaning and drying;

[0061] Among them, the preparation method of the high-conductivity composite electrolyte additive is as follows: weigh the corresponding raw materials according to the following weight ratio: lithium sulfate: aluminum sulfate: germanium sulfate: silicon dioxide: pure water = 0.95:2.95:2:5.1:8.1, add lithium sulfate, aluminum sulfate, germanium sulfate, and silicon dioxide to pure water according to the above proportions, and use a high-speed shearing machine for shearing at room temperature. The high-speed shearing process parameters are 4000-6000rpm, 20-40min, and the preparation of the high-conductivity composite electrolyte additive is completed.

[0062] Example 2

[0063] A formula for a high charge acceptance-rich auxiliary battery plate and an auxiliary battery manufacturing process, wherein the positive lead paste formula comprises the following components in parts by weight:

[0064]

[0065] The positive electrode and paste process is:

[0066] 1) Sodium peroxide, antimony trioxide, ultra-short fibers and lead powder are dry-mixed, and deionized water accounting for 28% of the total mass of deionized water is added, the water adding time is controlled within 1.8 minutes, and the mixture is stirred for 4 minutes;

[0067] 2) Add the remaining deionized water for 3 minutes and continue stirring for 5 minutes;

[0068] 3) Then add 1.38g / cm 3 Dilute sulfuric acid solution, the acid addition time is controlled within 9 minutes;

[0069] 4) Finally, open the cooling system, continue stirring, and cool down to 50°C to obtain the positive electrode lead paste;

[0070] The negative electrode lead paste formula contains the following components in parts by weight:

[0071]

[0072] The negative electrode and paste process is:

[0073] 1) First, mix the ultrafine barium sulfate, Norwegian lignin, ultrashort fibers and lead powder, add deionized water accounting for 27% of the total mass of deionized water, add for 2.5 minutes, and stir for 3.5 minutes;

[0074] 2) Add the remaining deionized water for 4 minutes and continue stirring for 7 minutes;

[0075] 3) Then add 1.38g / cm 3 Dilute sulfuric acid solution, the acid addition time is controlled within 9 minutes;

[0076] 4) Finally, open the cooling system, continue stirring, and cool down to 50°C to obtain the negative electrode lead paste.

[0077] The lead paste is transferred to the paste coating hopper and evenly coated on the surface of the grid strip by the paste coating machine, and then the grid strip is cut to produce a single wet plate. The single wet plate is quickly dried in a drying kiln and then transferred to a curing drying chamber, and cured and dried into a dry raw plate through a curing and drying process;

[0078] The pole group encapsulation uses PE separator to encapsulate the negative electrode;

[0079] The battery is assembled using a COS casting welding machine. The ends of the encapsulated and assembled pole group ears are immersed in a mold filled with molten lead. The positive and negative plate ears are quickly cast and welded in parallel. The welded pole groups are then loaded into the battery tank. A high current is applied to the connectors of the positive and negative pole groups through the through-wall welding machine fixture to partially melt the connectors. The pressure is maintained for 3 seconds, and the adjacent connectors are welded together and distributed into each single cell of the battery tank. The pole groups are butt-welded using a butt welding process, and then the large cover is heat-sealed.

[0080] Battery formation: A dilute sulfuric acid solution is used for primary acid addition. 10% of a highly conductive composite electrolyte additive is added to the dilute sulfuric acid electrolyte for primary acid addition. The composition and weight ratio of the composite electrolyte additive are (lithium sulfate: aluminum sulfate: germanium sulfate: silicon dioxide: pure water = 1:3.1:2.1:5.2:8.0). An intermittent constant current charging formation process is used for charging formation. After the formation, a non-reversing acid process is used. Only each cell of the battery tank is acidified for a second time. The liquid level is adjusted. The final electrolyte mixed acid density is 1.283 g / cm 3 , and finally the small cover is heat-sealed, air-tightness tested, and finally the high current test and battery cleaning and drying are carried out.

[0081] Example 3

[0082] A formula for a high charge acceptance-rich auxiliary battery plate and an auxiliary battery manufacturing process, wherein the positive lead paste formula comprises the following components in parts by weight:

[0083]

[0084] The positive electrode and paste process is:

[0085] 1) Sodium peroxide, antimony trioxide, ultra-short fibers and lead powder are dry-mixed, and deionized water accounting for 29% of the total mass of deionized water is added. The water adding time is controlled within 2 minutes, and the mixture is stirred for 3.5 minutes;

[0086] 2) Add the remaining deionized water for 3.5 minutes and continue stirring for 6 minutes;

[0087] 3) Then add 1.38g / cm 3 Dilute sulfuric acid solution, the acid addition time is controlled within 9 minutes;

[0088] 4) Finally, open the cooling system, continue stirring, and cool down to 50°C to obtain the positive electrode lead paste;

[0089] The negative electrode lead paste formula contains the following components in parts by weight:

[0090]

[0091] The negative electrode and paste process is:

[0092] 1) First, mix LN-01 composite additive, ultrafine barium sulfate, Norwegian lignin, ultrashort fibers and lead powder, add deionized water accounting for 28% of the total mass of deionized water, add for 2.5 minutes, and stir for 4 minutes;

[0093] 2) Add the remaining deionized water for 4 minutes and continue stirring for 8 minutes;

[0094] 3) Then add 1.38g / cm 3 Dilute sulfuric acid solution, the acid addition time is controlled within 9 minutes;

[0095] 4) Finally, open the cooling system, continue stirring, and cool down to 50°C to obtain the negative electrode lead paste.

[0096] The lead paste is transferred to the paste coating hopper and evenly coated on the surface of the grid strip by the paste coating machine, and then the grid strip is cut to produce a single wet plate. The single wet plate is quickly dried in a drying kiln and then transferred to a curing drying chamber, and cured and dried into a dry raw plate through a curing and drying process;

[0097] The pole group encapsulation uses PE separator to encapsulate the negative electrode;

[0098] The battery is assembled using a COS casting welding machine. The ends of the encapsulated and assembled pole group ears are immersed in a mold filled with molten lead. The positive and negative plate ears are quickly cast and welded in parallel. The welded pole groups are then loaded into the battery tank. A high current is applied to the connectors of the positive and negative pole groups through the through-wall welding machine fixture to partially melt the connectors. The pressure is maintained for 4 seconds, and the adjacent connectors are welded together and distributed into each single cell of the battery tank. The pole groups are butt-welded using a butt welding process, and then the large cover is heat-sealed.

[0099] Battery formation: A dilute sulfuric acid solution is used for primary acid addition. 12% of a highly conductive composite electrolyte additive is added to the dilute sulfuric acid electrolyte for primary acid addition. The composition and weight ratio of the composite electrolyte additive are (lithium sulfate: aluminum sulfate: germanium sulfate: silicon dioxide: pure water = 1.1: 3.0: 2.1: 5.0: 8.0). An intermittent constant current charging formation process is used for charging formation. After the formation is completed, a non-reversing acid process is used. Only each cell of the battery tank is acidified for a second time. The liquid level is adjusted. The final electrolyte mixed acid density is 1.282 g / cm 3 , and finally the small cover is heat-sealed, air-tightness tested, and finally the high current test and battery cleaning and drying are carried out.

[0100] Example 4

[0101] A formula for a high charge acceptance-rich auxiliary battery plate and an auxiliary battery manufacturing process, wherein the positive lead paste formula comprises the following components in parts by weight:

[0102]

[0103] The positive electrode and paste process is:

[0104] 1) Dry-mix sodium peroxide, antimony trioxide, ultra-short fibers and lead powder, add deionized water accounting for 30% of the total mass of deionized water, control the water addition time to 2 minutes, and stir for 4 minutes;

[0105] 2) Add the remaining deionized water for 4 minutes and continue stirring for 6 minutes;

[0106] 3) Then add 1.38g / cm 3 Dilute sulfuric acid solution, the acid addition time is controlled within 9 minutes;

[0107] 4) Finally, open the cooling system, continue stirring, and cool down to 50°C to obtain the positive electrode lead paste;

[0108] The negative electrode lead paste formula contains the following components in parts by weight:

[0109]

[0110]

[0111] The negative electrode and paste process is:

[0112] 1) First, mix LN-01 composite additive, ultrafine barium sulfate, Norwegian lignin, ultrashort fibers and lead powder, add deionized water accounting for 28% of the total mass of deionized water, add for 2 minutes, and stir for 4 minutes;

[0113] 2) Add the remaining deionized water for 4 minutes and continue stirring for 7.5 minutes;

[0114] 3) Then add 1.38g / cm 3 Dilute sulfuric acid solution, the acid addition time is controlled within 9 minutes;

[0115] 4) Finally, open the cooling system, continue stirring, and cool down to 50°C to obtain the negative electrode lead paste.

[0116] The lead paste is transferred to the paste coating hopper and evenly coated on the surface of the grid strip by the paste coating machine, and then the grid strip is cut to produce a single wet plate. The single wet plate is quickly dried in a drying kiln and then transferred to a curing drying chamber, and cured and dried into a dry raw plate through a curing and drying process;

[0117] The pole group encapsulation uses PE separator to encapsulate the negative electrode;

[0118] The battery is assembled using a COS casting welding machine. The ends of the encapsulated and assembled pole group ears are immersed in a mold filled with molten lead. The positive and negative plate ears are quickly cast-welded in parallel. The welded pole groups are then loaded into the battery tank. A high current is applied to the connectors of the positive and negative pole groups through the through-wall welding machine fixture to partially melt the connectors. The pressure is maintained for 5 seconds, and the adjacent connectors are welded together and distributed into each single cell of the battery tank. The pole groups are butt-welded using a butt welding process, and then the large cover is heat-sealed.

[0119] Battery formation: The first acid addition is carried out with conventional dilute sulfuric acid solution, without adding composite electrolyte additives, and the intermittent constant current charging formation process is used for charging formation. After the formation, the non-reversing acid process is used, and only the secondary acid is added to each cell of the battery tank to adjust the liquid level. The final electrolyte mixed acid density is 1.280g / cm 3 , and finally the small cover is heat-sealed, air-tightness tested, and finally the high current test and battery cleaning and drying are carried out.

[0120] Example 5

[0121] A formula for a high charge acceptance-rich auxiliary battery plate and an auxiliary battery manufacturing process, wherein the positive lead paste formula comprises the following components in parts by weight:

[0122]

[0123]

[0124] The positive electrode and paste process is:

[0125] 1) Sodium peroxide, antimony trioxide, ultra-short fibers and lead powder are dry-mixed, and deionized water accounting for 30% of the total mass of deionized water is added. The water adding time is controlled within 2 minutes and the mixture is stirred for 4 minutes;

[0126] 2) Add the remaining deionized water for 4 minutes and continue stirring for 6 minutes;

[0127] 3) Then add 1.38g / cm 3 Dilute sulfuric acid solution, the acid addition time is controlled within 10 minutes;

[0128] 4) Finally, open the cooling system, continue stirring, and cool down to 50°C to obtain the positive electrode lead paste;

[0129] The negative electrode lead paste formula contains the following components in parts by weight:

[0130]

[0131] The negative electrode and paste process is:

[0132] 1) First, mix LN-01 composite additive, ultrafine barium sulfate, Norwegian lignin, ultrashort fibers and lead powder, add deionized water accounting for 29% of the total mass of deionized water, add for 2 minutes, and stir for 3 minutes;

[0133] 2) Add the remaining deionized water for 4 minutes and continue stirring for 8 minutes;

[0134] 3) Then add 1.38g / cm 3 Dilute sulfuric acid solution, the acid addition time is controlled within 9 minutes;

[0135] 4) Finally, open the cooling system, continue stirring, and cool down to 50°C to obtain the negative electrode lead paste.

[0136] The lead paste is transferred to the paste coating hopper and evenly coated on the surface of the grid strip by the paste coating machine, and then the grid strip is cut to produce a single wet plate. The single wet plate is quickly dried in a drying kiln and then transferred to a curing drying chamber, and cured and dried into a dry raw plate through a curing and drying process;

[0137] The pole group encapsulation uses PE separator to encapsulate the negative electrode;

[0138] The battery is assembled using a COS casting welding machine. The ends of the encapsulated and assembled pole group ears are immersed in a mold filled with molten lead. The positive and negative plate ears are quickly cast-welded in parallel. The welded pole groups are then loaded into the battery tank. A high current is applied to the connectors of the positive and negative pole groups through the through-wall welding machine fixture to partially melt the connectors. The pressure is maintained for 5 seconds, and the adjacent connectors are welded together and distributed into each single cell of the battery tank. The pole groups are butt-welded using a butt welding process, and then the large cover is heat-sealed.

[0139] Battery formation: A dilute sulfuric acid solution is used for primary acid addition. 20% of a highly conductive composite electrolyte additive is added to the dilute sulfuric acid electrolyte for primary acid addition. The composition and weight ratio of the composite electrolyte additive are (lithium sulfate: aluminum sulfate: germanium sulfate: silicon dioxide: pure water = 1.1:2.9:2.1:5.1:8.0). An intermittent constant current charging formation process is used for charging formation. After the formation, a non-reversing acid process is used. Only each cell of the battery tank is supplemented with acid for the second time. The liquid level is adjusted. The final electrolyte mixed acid density is 1.281 g / cm 3 , and finally the small cover is heat-sealed, air-tightness tested, and finally the high current test and battery cleaning and drying are carried out.

[0140] The performance of the auxiliary batteries prepared in the above Examples 1-5 and conventional flooded auxiliary batteries of the same type were tested, and the test results are listed in Table 1.

[0141] Among them, the deep discharge low voltage charging acceptance test method is:

[0142] a. After the battery is fully charged (charged at 25℃±1℃ with a current of 2In(A) until the average voltage of the single battery reaches 2.4V, and then continue charging for 5h), within 1 to 5h, and kept at an ambient temperature of 25℃±2℃, discharge at a current of Io(A) for 5h (I0=Ce / 10).

[0143] b. After discharge, immediately place the battery in a low-temperature box or low-temperature room at 0°C for at least 20 hours.

[0144] c. The battery should be charged at 14.00V±0.1V within 1 minute after being taken out of the low-temperature box. After 10 minutes, the charging current Ica (A) should be recorded and the Ica / I0 ratio should be calculated, which should be ≥2.0.

[0145] Table 1 Performance test results of the prepared auxiliary battery

[0146]

[0147]

[0148] It can be seen from the data in Table 1 that the charging acceptance performance of the auxiliary battery prepared by Example 2 is higher than that of Example 1, indicating that adding sodium peroxide oxygen enhancer in the positive electrode lead paste formula can improve the deep discharge low-voltage charging acceptance performance of the auxiliary battery; the charging acceptance performance of the auxiliary battery prepared by Example 3 is higher than that of Example 2, indicating that adding LN-01 composite additive in the negative electrode lead paste formula can improve the deep discharge low-voltage charging acceptance performance of the battery; the charging acceptance performance of the auxiliary battery prepared by Example 5 is higher than that of Example 4, indicating that adding composite electrolyte additives in the electrolyte can improve the deep discharge low-voltage charging acceptance capacity of the auxiliary battery.

[0149] The above description is only 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 principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A process for manufacturing a flooded auxiliary battery with high charge acceptance performance, characterized in that: The following steps are involved: Preparation of positive electrode lead paste: The positive electrode lead paste formula comprises the following components in parts by weight: Lead powder 100 parts, 5-9 parts of sulfuric acid, 9-13 parts of deionized water, Antimony trioxide 0.06-0.12 parts, Oxygen enhancer 0.2-0.6 parts, Ultrashort fibers 0.06-0.12 parts; The oxygen promoter is used to release oxygen during the plate curing process to form an oxidized corrosion layer at the grid interface; Preparation of negative electrode lead paste: The negative electrode lead paste formula comprises the following components in parts by weight: Lead powder 100 parts, 6-11 parts of sulfuric acid, 8-13 parts of deionized water, Ultrashort fibers 0.06-0.10 parts, LN-01 composite additive 0.2~0.4 parts, Superfine barium sulfate 0.5-1.1 parts, Norwegian lignin 0.1-0.3 parts; Plate preparation: Lead paste is evenly applied to the surface of the grid strip, and then the grid strip is cut to produce a single wet plate. The single wet plate is quickly dried in a drying kiln and then transferred to a curing and drying chamber, where it is cured and dried into a dry raw plate through a curing and drying process; Pole group encapsulation: The negative electrode is encapsulated with a separator; Battery assembly: Immerse the ends of the encapsulated and assembled pole group ears into a mold filled with molten lead, quickly cast and weld the positive and negative plate ears in parallel, then load the welded pole group into the battery tank, weld the adjacent connectors together, distribute them into each cell of the battery tank, use the butt welding process to butt weld the pole group, and then heat seal the large cover; Battery formation: A dilute sulfuric acid solution is used for primary acid addition. 10% to 20% of a high-conductivity composite electrolyte additive is added to the dilute sulfuric acid electrolyte for primary acid addition. The composition and weight ratio of the high-conductivity composite electrolyte additive are lithium sulfate: aluminum sulfate: germanium sulfate: silicon dioxide: pure water = (1±0.1): (3±0.2): (2±0.2): (5±0.3): (8±0.5). An intermittent constant current charging formation process is used for charging formation. After the formation, a non-reversing acid process is used. Only a small amount of acid is added to each cell of the battery tank for a second time to adjust the liquid level and ensure that the electrolyte mixed acid density is 1.280±0.005g / cm 3 .

2. The process for manufacturing a flooded auxiliary battery with high charge acceptance according to claim 1, characterized in that: The paste making process of the positive electrode lead paste is as follows: 1) Weigh the raw materials according to the weight of the positive electrode formula; dry-mix sodium peroxide, antimony trioxide, ultra-short fibers and lead powder, add deionized water accounting for 25-35% of the total mass of deionized water, control the water addition time to 1-2 minutes, and stir for 2-4 minutes; 2) Add the remaining deionized water, control the water addition time to 3-4 minutes, and continue stirring for 3-6 minutes; 3) Then add 1.38g / cm 3 For dilute sulfuric acid solution, the acid addition time should be controlled within 7 to 10 minutes; 4) Finally, open the cooling system, continue stirring, and cool down to 50±3°C to obtain the positive electrode lead paste.

3. The process for manufacturing a flooded auxiliary battery with high charge acceptance according to claim 1, characterized in that: The paste preparation process of the negative electrode lead paste is as follows: 1) Weigh the raw materials according to the weight of the negative electrode formula; stir and mix the LN-01 composite additive, ultrafine barium sulfate, Norwegian lignin, ultrashort fibers and lead powder, add deionized water accounting for 25-35% of the total mass of deionized water, control the addition time to 1.5-2.5 minutes, and stir for 2-4 minutes; 2) Add the remaining deionized water, control the water addition time to 3-4 minutes, and continue stirring for 5-10 minutes; 3) Then add 1.38g / cm 3 For dilute sulfuric acid solution, the acid addition time should be controlled within 7 to 10 minutes; 4) Finally, open the cooling system, continue stirring, and cool down to 50±3℃ to obtain the negative electrode lead paste.

4. The process for manufacturing a flooded auxiliary battery with high charge acceptance according to claim 1, characterized in that: The oxygen-promoting agent is sodium peroxide, and the crystal size of the sodium peroxide is 1.5-4 μm.

5. The process for manufacturing a flooded auxiliary battery with high charge acceptance according to claim 1, characterized in that: The LN-01 composite additive is a composite crystal obtained by ball milling lead sulfate crystals and activated carbon in a weight ratio of (1±0.2):(1±0.2). The particle size of the composite crystal is 1.5-4.5 μm.

6. The process for manufacturing a flooded auxiliary battery with high charge acceptance according to claim 1, characterized in that: The separator is a PE separator.

7. The process for manufacturing a flooded auxiliary battery with high charge acceptance according to claim 1, characterized in that: The preparation method of the high-conductivity composite electrolyte additive is as follows: weigh the corresponding raw materials according to the following weight ratio: lithium sulfate: aluminum sulfate: germanium sulfate: silicon dioxide: pure water = (1±0.1): (3±0.2): (2±0.2): (5±0.3): (8±0.5), add lithium sulfate, aluminum sulfate, germanium sulfate, and silicon dioxide to pure water according to the above ratio, and use a high-speed shearing machine for shearing at room temperature. The high-speed shearing process parameters are 4000-6000rpm, 20-40min, and the preparation of the high-conductivity composite electrolyte additive is completed.

8. The process for manufacturing a flooded auxiliary battery with high charge acceptance according to claim 1, characterized in that: The battery formation process also includes heat sealing of the small cover after adjusting the liquid level, air tightness testing, and finally high current testing and battery cleaning and drying.

9. The process for manufacturing a flooded auxiliary battery with high charge acceptance according to claim 1, characterized in that: The specific method of welding adjacent connectors together in the battery assembly is as follows: applying a high current to the connectors of the positive and negative electrode groups through a through-wall welding machine fixture to partially melt the connectors and maintain pressure for 3-5 seconds.

10. A flooded auxiliary battery prepared by the manufacturing process of a flooded auxiliary battery with high charge acceptance performance according to any one of claims 1 to 9.

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