A colloidal battery restorer and method of use thereof

Abstract

The application discloses a colloidal battery repairing agent and a preparation method thereof. The colloidal battery repairing agent has the characteristics of low electrolyte density, less active material falling and long service life. The colloidal battery repairing agent is prepared by using a powder and a solvent, and is configured on site. The colloidal battery repairing agent is prepared from natural magnesium-rich silicate ore, modified serpentine and 8-hydroxyquinoline (HQ). The solvent is obtained by combining nano carbon particles, N-(2-hydroxyethyl) acrylamide, sodium sulfate, potassium sulfate and deionized water. The colloidal battery repairing agent can reduce the internal resistance of the colloidal battery, and can make the colloidal battery with a nominal capacity of 50% or more meet the requirement of a nominal capacity of 80% or more after repair, so that the colloidal battery meets the qualified requirement and the service life of the colloidal battery is prolonged.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of gel battery repair, and relates to a gel battery repair agent and a use method thereof. BACKGROUND

[0002] In the discharging process of the gel battery, PbSO4 with low solubility and non-steady state is generated, which will continuously precipitate in the form of crystals after reaching saturation. The PbSO4 generated in the normal discharging process is uniformly distributed on the plates of the battery in the form of small crystalline particles, and can be more easily reduced to Pb and PbO2 during charging. As is known to all, all redox reactions cannot be 100% conducted, therefore, with the accumulation of time, part of the PbSO4 cannot be fully reduced to the sponge-like Pb, and these PbSO4 gradually accumulates, gradually forms a steady state from a non-problem, forms crystals with a diameter of 10-50 μm, and finally blocks the micropores of the plates and the separators, hinders the penetration of the electrolyte, and finally increases the internal resistance of the battery and reduces the charging acceptance capacity of the battery. When the storage temperature is relatively high, the float voltage is too low during use, the initial charging is insufficient, the charging is often insufficient, or the battery is deeply discharged, etc., the sulfation rate of the gel battery will be faster, and when the sulfation reaches a certain degree, the battery can only be scrapped. The formation of the steady-state PbSO4 crystals leads to the reduction of the electrochemical reaction substances of the gel battery, which is also the main reason for the failure and performance degradation of the gel battery.

[0003] Therefore, how to inhibit and eliminate sulfation and maximize the service life of the gel battery pack is an important topic that everyone is struggling to research and urgently needs to be solved. A large number of studies have confirmed that adding a repair agent, which is in line with the characteristics of the gel battery, heating, and the catalytic decomposition of lead sulfate particles in the environment, is an effective way to restore the performance of the gel battery and improve the charge-discharge cycle performance. However, due to the characteristics of the structure of the gel battery and the low density of the electrolyte of the gel battery, the repair technology of the gel battery has developed slowly.

[0004] Serpentine is a layered silicate mineral, and its ideal molecular formula is Mg6(Si4O 10 8(OH)8. The crystal structure of serpentine is a tri-octahedral type, which is composed of a magnesium hydroxide octahedral layer and a silicon oxygen tetrahedral layer, and a small amount of Mg 2+ in the crystal can be replaced by metal ions such as Fe 2+ , Cr 2+ , Mn 2+ , Ni 2+ , etc. There are also unsaturated Si-O-Si, O-Si-O bonds and magnesium bonds on the fracture surface of serpentine, which makes serpentine have high chemical activity. In addition, serpentine has abundant reserves and high specific surface area, but at present it is mainly used as a potential adsorbent for heavy metal pollution in water and soil, and natural serpentine has no effect on Pb2+ The adsorption performance of the colloidal battery is limited, and how to further improve the adsorption performance is a problem to be solved for the colloidal battery.

[0005] The filling process of the colloidal battery is a bridge between the electrolyte and the battery, and the filling is not simply filling the electrolyte into the battery. If the filling process is not properly selected, even if a colloidal electrolyte with excellent performance is used, the performance of the colloidal battery will deteriorate. Whether the filling process of the colloidal electrolyte is reasonable is related to the comprehensive performance of the colloidal battery. SUMMARY

[0006] The technical problem to be solved by the present application is to prepare a colloidal battery repair agent which can restore the performance of a deteriorated colloidal battery and promote the activation and regeneration of a colloidal battery with degraded performance to prolong the service life of the colloidal battery.

[0007] The first aspect of the present application provides a colloidal battery repair agent, comprising:

[0008] A repair powder prepared from a natural magnesium-rich silicate ore, modified serpentine and 8-hydroxyquinoline;

[0009] A mixture of nano-carbon particles, N-(2-hydroxyethyl) acrylamide, sodium sulfate and potassium sulfate;

[0010] And deionized water;

[0011] The natural magnesium-rich silicate ore, modified serpentine and 8-hydroxyquinoline are mixed in a mass ratio of 10:1:0.1, and the mixed material is placed in a high-temperature kettle, the temperature is set at 1500-1700℃, heated, and cooled to obtain a repair powder; the mixture of the natural magnesium-rich silicate ore, modified serpentine and 8-hydroxyquinoline is heated in the high-temperature kettle for 0.5-2 hours. The inventors of the present application have found that the powder can obtain a larger specific surface area under high temperature, and the powder has stronger activity.

[0012] The nano-carbon particles, N-(2-hydroxyethyl) acrylamide, sodium sulfate and potassium sulfate are mixed in a ratio of 1:1:5:5 to obtain a mixture;

[0013] The mixture is added to deionized water in a percentage of 0.01-0.03% of the mass of the deionized water, and then 0.01-0.03% of the mass of the deionized water of the repair powder is added, and the mixture is uniformly mixed to obtain a colloidal battery repair agent;

[0014] The preparation method of the modified serpentine is:

[0015] S1: the natural serpentine is activated at high temperature, cooled, ground, sieved to obtain natural serpentine powder, then stirred with water, and then the cysteamine hydrochloride is added and stirred magnetically, and then the mixture is left to stand, washed with deionized water, and dried to obtain the organic serpentine; wherein the mass ratio of the natural serpentine powder to the cysteamine hydrochloride is 100g:6g;

[0016] The natural serpentine is from a serpentine mine in Gansu, and the particle size of the sample prepared after crushing and ball milling is 200 mesh, and the chemical formula of the serpentine is Mg3Si2O5(OH)4. The XRF results and the theoretical amount of the components are MgO 43.6%, SiO2 43.6%, and H2O 13.1%, respectively.

[0017] The natural serpentine is activated at high temperature, and the natural serpentine can be activated in a crucible in a muffle furnace at an activation temperature of 400-600℃ for 40-60min; the sieving is 100-150 mesh; the magnetic stirring time in step S1 is 1-2h, and the magnetic stirring time in step S3 is 1-2h; the drying temperature in step S1 is 60-70℃;

[0018] S2: 0.1mol·L -1 Na2CO3 solution is mixed with 0.1 mol·L -1 FeCl3·6H2O at a volume ratio of 1:2, and a polyhydroxy iron polymer solution is prepared by magnetic stirring,

[0019] S3: the organic serpentine in S1 is mixed with deionized water to prepare a 500g·L -1 organic serpentine slurry, and then the polyhydroxy iron polymer solution in S2 is added, and the mixture is stirred magnetically, left to stand, and washed to obtain the modified serpentine; the volume ratio of the organic serpentine slurry to the polyhydroxy iron polymer solution is 3:2.

[0020] Further, the nano-carbon particles have a particle size of ≤50nm and a resistivity of ≤5×10 -4 Ω.cm.

[0021] Another aspect of the present application provides a method for using a colloidal battery repair agent, which is divided into two kinds: the first kind is to directly add the colloidal battery repair agent into the battery electrolyte, and then perform filling to prepare a colloidal battery; the second kind is to directly add the colloidal battery repair agent into the battery electrolyte through the valve opening of the colloidal battery when the electrolyte of the colloidal battery has been filled. In the first case:

[0022] (1) first add the colloidal battery repair agent into the electrolyte, before filling, first stir the electrolyte added with the colloidal battery repair agent, the stirring speed is 800r / min-1200r / min, at room temperature, use direct filling method to fill the battery, the filling speed is 30-45mL / min;

[0023] The inventor of the present application finds through research that as the stirring speed increases, the distribution of the colloidal electrolyte is more uniform, so it is understandable that the cycle life of the battery made at a stirring speed of 800r / min is longer than that at a stirring speed lower than 800r / min. However, the cycle life at a stirring speed higher than 1200r / min is shorter than that at 800r / min, which may be because when the stirring speed is 1200r / min, the speed is too high, the gel molecules are destroyed under high-speed stirring, the colloidal particles are dispersed, large particles gradually become small particles, and small particles become even smaller. These small particles are prone to release water during the gelation in the cycle process, which will affect the final cycle life over a long period of time. Therefore, the stirring speed of 800r / min-1200r / min is a relatively appropriate choice.

[0024] The inventor of the present application also finds through research that at room temperature, the direct filling method for battery filling is more uniform in the distribution of colloidal electrolyte and has a longer cycle life than high temperature or over-discharge method. Although the initial capacity of the over-discharge method is larger, the capacity decays rapidly, and the discharge capacity from the 27th time to the end of life is less than that of the direct filling method. Therefore, the filling method is selected as the direct filling method at room temperature.

[0025] The inventor of the present application also finds through research that when the filling speed is less than 30mL / min, the initial discharge capacity of the colloidal battery increases as the filling speed decreases. However, it is not conducive to industrial production. At the same time, when filling the colloidal electrolyte into the battery tank, a large amount of gas will be generated. If the electrolyte is injected quickly, a large amount of electrolyte will block the gas discharge channel, making it difficult for the gas to be discharged, which will increase the internal resistance of the battery made and reduce the discharge capacity. Therefore, the electrolyte should be injected at an appropriate speed to give the gas sufficient time and space to discharge. Of course, the filling speed cannot be too slow, which not only has a higher requirement on the gelation time of the colloidal electrolyte, but also affects the speed of industrial production. Therefore, the filling speed of 30-45mL / min is a relatively appropriate speed.

[0026] (2) After injecting the electrolyte, the battery is first placed, and then the battery is activated by charging and discharging; after the charging and discharging activation is completed, the battery is secondly placed, and the performance test is prepared.

[0027] Further, the stirring time is 15-25min, and the first and second battery standing times are both 5-24 hours.

[0028] The second case: when the electrolyte of the gel battery has been filled, the gel battery repair agent is directly added into the electrolyte of the battery through the valve port of the gel battery.

[0029] A method for using the gel battery repair agent, the gel battery repair agent is heated to 75-85 DEG C, and is added into the electrolyte of the gel battery through the valve port of the gel battery by using a direct filling method, and then the battery is subjected to charge-discharge activation, and after the charge-discharge activation is completed, the battery is secondarily rested, and is prepared for performance test.

[0030] Further, the added amount of the gel battery repair agent is 0.5 ml of the gel battery repair agent per surface capacity AH of the gel battery.

[0031] Further, the charge-discharge activation is a charge-discharge cycle process, the charge voltage is less than 2.85 V, and the charge current is 0.02C-0.2C, and the battery is in a charged state; the charge voltage is greater than or equal to 2.85 V, or the charge current is less than 0.02C, and the battery is in a discharged state.

[0032] Further, the charge-discharge cycle process is repeated at most 2 times.

[0033] The present application has the following advantages and effects relative to the prior art:

[0034] (1) The repair agent obtained in this invention is a nanotube material with a unique tubular structure. Its outer diameter is generally 11-85 nm, mostly in the range of 20-50 nm, while the inner diameter is 2-25 nm, mostly less than 10 nm. The repair agent has excellent mechanical strength and heat resistance, and also has high surface chemical activity. Its activity mainly comes from the unsaturated bonds on the surface, the high surface energy brought about by the huge specific surface area of ​​the nanocrystals, and the additional internal and surface energy caused by the lattice bending due to the curled structure. The excellent physical and chemical properties enable it to function in the acidic environment of gel batteries; among them, the unsaturated bonds, especially oxygen containing uncoupled electrons, suspended silicon, and hydroxyl (OH-) on the fiber surface have the strongest surface activity. This repair agent also has a positive effect on Pb. 2+ It exhibits strong adsorption properties, which are achieved through its hydroxyl groups and unsaturated Si-O-Si bonds. The oxygen exposed by the broken Si-O-Si bonds can react with Pb. 2+ Plasma bonding, under the influence of external electrons, promotes the decomposition of lead sulfate. This invention is a further development based on existing technology. The inventors discovered that natural serpentine, through modification, is first activated at high temperature, cooled, ground, and sieved to obtain natural serpentine powder. Then, it is modified with cysteine ​​hydrochloride and a polyhydroxy iron polymer solution, a combination of inorganic and organic methods. The inventors' research shows that the specific surface area and pore size of the modified serpentine are larger than those before modification. This increase in pore size and specific surface area provides more adsorption sites and space for heavy metal adsorption. Simultaneously, natural magnesium-rich silicate ore, modified serpentine, and 8-hydroxyquinoline are mixed in a mass ratio of 10:1:0.1. The mixed material is placed in a high-temperature autoclave at 1500-1700℃, heated, and cooled to obtain a repair powder. Under high temperature conditions, the specific surface area of ​​the colloidal battery repair agent is further increased, giving the powder stronger activity. Therefore, modified serpentine adsorbs Pb 2+ The ability of modified serpentine to adsorb Pb is greatly enhanced, accelerating the decomposition of lead sulfate and improving the repair efficiency of the repair agent. The inventors believe that modified serpentine adsorbs Pb... 2+ The mechanism is mainly Pb 2+ The modified serpentine binds to high-energy bonds formed on its surface, adsorbing as Pb(NO3)2·Si-O and PbO·O-Si-O complexes on the serpentine surface. The modified serpentine in solution contains Pb... 2+ Both the desorption capacity and desorption rate of modified serpentine are high, indicating that modified serpentine has a high effect on the desorption of Pb. 2+ The adsorption of Pb is relatively stable. 2+ It is not easily desorbed.

[0035] (2) The present application first solves the problem of repairing the gel battery, effectively solving the problem of increased internal resistance and decreased capacity of the gel battery caused by sulfation. Because the sulfuric acid density of the gel battery electrolyte is low, the electron transfer speed is slow, and the chemical reaction is not active, the normal repair technology cannot realize the repair of the gel battery. The use of a heated repair solution, high voltage and large current, allows the internal chemical reaction conditions of the repaired battery to be more sufficient, with higher repair rate and repair efficiency.

[0036] (3) The present repair agent and method of use essentially achieve a decrease in the internal resistance of the gel battery, restoring the redox reaction capability of the battery without any destructive materials and repair process. BRIEF DESCRIPTION OF DRAWINGS

[0037] Figure 1 is the discharge curve of the battery before repair in the application example of the present application.

[0038] Figure 2 is the discharge curve of the battery after repair in the application example of the present application.

[0039] Figure 3 is the discharge curve of the battery after repair in the application example of the present application. DETAILED DESCRIPTION

[0040] In order to make the technical means and achieve the purpose and effect of the present application easy to understand, the following will be further illustrated in combination with specific examples.

[0041] According to the material and implementation method provided by the present application, we configure the powder and solvent for repairing the gel battery.

[0042] Example 1:

[0043] Preparation of modified serpentine:

[0044] Take 500 g of natural serpentine in a crucible and heat activate it in a muffle furnace at 500℃ for 50 min. After cooling, grind it to 100 mesh. Take 100 g of natural serpentine powder and stir it evenly in 200 mL of distilled water. Add 300 mL of 20 g·L -1 Cysteamine hydrochloride solution is stirred magnetically for 2 h, washed with deionized water for 5 times, and dried at 60℃ to obtain organic serpentine, which is named as organic modified serpentine. Take 100 mL of 0.1 mol·L -1 Na2CO3 solution and 200 mL of 0.1 mol·L -1FeCl3·6H2O, magnetic stirring 1h standby, take 1L beaker 200mL water and 100g organic serpentine magnetic stirring 1h, 300mL polyhydroxy iron polymer solution is added to 200mL organic serpentine slurry magnetic stirring 2h, after standing with deionized water 5 times, named organic and inorganic combined modified serpentine, that is, the modified serpentine claimed in the application.

[0045] Pore size and specific surface area analysis

[0046] In order to explore the change of pore size and specific surface area of modified serpentine, the specific surface area and porosity analyzer is used to determine the change before and after modification, and table 1 is the pore size and specific surface area analysis result.

[0047] Table 1 pore size and specific surface area analysis of modified serpentine

[0048]

[0049] Comparing the specific surface area and pore size analysis data of natural serpentine before and after modification in table 1, the BET specific surface area of inorganic and organic combined modified serpentine increases from 9.17 to 14.16m 2 ·g -1 , the specific surface area increases by 54.4%, the specific surface area of organic modification increases to 11.37m 2 ·g -1 , the specific surface area increases by 24%. Compared with unmodified natural serpentine, the pore volume of organic modified serpentine and inorganic and organic combined modified serpentine is basically unchanged. Compared with unmodified serpentine, the pore size of organic modified serpentine and inorganic and organic combined modified serpentine increases from 3.03 nm to 3.81 nm and 3.82 nm respectively. Organic modification and inorganic and organic combined modification both increase the specific surface area and pore size of serpentine, and the increase of pore size and specific surface area provides more adsorption sites and space for heavy metal adsorption.

[0050] Example 2;

[0051] The preparation method of colloidal battery repair agent and the colloidal battery repair agent prepared according to the method:

[0052] The natural magnesium-rich silicate ore, modified serpentine and 8-hydroxyquinoline are mixed in a mass ratio of 10:1:0.1, and the mixed material is placed in a high temperature kettle, the temperature is set at 1600℃, heated, and cooled to obtain the repair powder; the mixture of natural magnesium-rich silicate ore, modified serpentine and 8-hydroxyquinoline is heated in the high temperature kettle for 1 hour. The inventor of the application finds that the powder can obtain a larger specific surface area under high temperature, and the powder has stronger activity.

[0053] (1) Take the mass percentage of 0.02 parts of repair powder, add 100 parts of deionized water to stir, form a transparent solution;

[0054] (2) The nano carbon particles, N-(2-hydroxyethyl) acrylamide, sodium sulfate and potassium sulfate are mixed in a ratio of 1:1:5:5 to obtain a mixture; take the mass percentage of 0.02 parts of the mixture into the transparent solution in the above step (1) to stir, form a translucent suspension, and obtain the colloidal battery repair agent. For the need of carrying, etc., we use a 300ml mineral water bottle to contain this repair agent, and each bottle contains 250ml.

[0055] Example 3:

[0056] A group of colloidal batteries from Guangzhou Power Supply Bureau of Southern Power Grid, a total of 24 2V colloidal batteries, colloidal batteries are German sunshine colloidal batteries, nominal capacity 500AH. The colloidal battery group has serious sulfuration before repair, and the capacity is only 325AH at 10-hour rate discharge.

[0057] According to the materials and implementation methods provided by the present application, the powder and solvent for repairing the colloidal battery in Example 2 are configured. Moreover, the powder and solvent have been mixed and injected into a transparent and scaled mineral water bottle. For the need of carrying, etc., we use a 300ml mineral water bottle to contain this repair agent, and each bottle contains 250ml.

[0058] The colloidal battery repair agent and its use method of the present application are added according to the battery capacity. The addition principle is to add 0.5ml of repair liquid per AH.

[0059] The nominal capacity of the colloidal battery in this case is 500AH, and a 250ml bottle of repair agent can just meet the needs of battery repair.

[0060] In actual use, a water tank is used for unified heating. This way is simple, efficient and fast. After heating to the specified temperature, the repair agent can be injected into the battery to start the battery repair.

[0061] The charge and discharge of battery repair can use a dedicated 2V charge and discharge device to independently charge and discharge the single battery. The 2V battery repair device needs to meet: output voltage 0-3V output, maximum output current greater than 100A.

[0062] A 6-battery monomer series can also be used to repair with a 12V charge and discharge device. The repair device meets: output voltage 0-20V, maximum current greater than 100A.

[0063] For this batch of storage battery repair, the battery is divided into 4 groups, each group of 6 batteries, and 4 repair machines are used for charging operation.

[0064] After the repair of the battery pack, the discharge capacity of the battery pack is 496AH at 10-hour rate, reaching 99.2% of the nominal capacity. The battery repair is successful once!

[0065] Before and after the battery repair, we selected No. 4 battery in the battery pack for comparison. Among them, Figure 1 The discharge curve before the battery repair in the application example of the application, Figure 1 In the application example, the battery performs 0.1C constant current discharge, and when the battery voltage drops below the discharge cutoff voltage of 1.8V, the battery capacity cannot meet the 80% capacity requirement. Figure 2 The discharge curve after the battery repair in the application example of the application, Figure 2 In the application example, the battery performs 0.1C constant current discharge, and when the battery voltage drops below the discharge cutoff voltage of 1.8V, the battery capacity meets the 100% capacity requirement.

[0066] Example 4:

[0067] Southern Power Grid Jiangmen Power Supply Bureau

[0068] A total of 24 2V gel batteries, gel batteries were put into use in 2008. Brand: German sunshine, nominal capacity 300AH. After testing, 24 gel batteries have no physical damage, and the whole group discharge capacity is 200AH after 10-hour discharge, which does not meet the 80% nominal capacity standard, and is determined as unqualified.

[0069] Add the repair agent of the application, add 0.5mL per 1AH, complete the repair agent injection of 24 battery monomers according to the configuration method of the repair agent and the injection process of the repair agent. The battery pack is charged and discharged in the whole group mode, and the battery pack is checked for capacity discharge to meet the requirement of 300AH, reaching 100% of the nominal capacity after 2 times of 0.1C complete charge and discharge operation.

[0070] Example 5:

[0071] The life evaluation of the battery repaired in Example 3:

[0072] In order to verify the battery life after repair, the high temperature float charging life experiment is carried out on the repaired battery. Two repaired gel batteries (repaired capacity 496 Ah and 500 Ah, original nominal capacity 500 Ah) are subjected to high temperature accelerated float charging aging test, the aging temperature is 58℃±2℃, the float charging voltage is set to 2.25V, every 30 days of continuous float charging, the battery is cooled to 25℃±2℃ under float charging state, and 3h rate and 10h rate discharge test is carried out, after 4 times of 30 days of high temperature float charging aging test, the capacity of the two gel batteries is 505 Ah and 510 Ah, and the discharge capacity meets the requirement of 100% of the nominal value. The test shows that the life of the repaired gel battery reaches 4 years.

[0073] Example 6:

[0074] The gel battery repair agent prepared in the above example 2 is added directly into the battery electrolyte, and then filled to prepare a gel battery according to the first case;

[0075] (1) The gel battery repair agent is first added to the electrolyte, which is generally fumed silica and sulfuric acid. In this embodiment, the silica content is 5% and the sulfuric acid content is 38%. It is a conventional technology in the art. Because the density of sulfuric acid in the gel battery electrolyte is low, the electron transfer speed is slow, and the chemical reaction is not active, the normal repair technology cannot realize the repair of the gel battery. When the gel battery repair agent is added to the electrolyte, the pore size of the modified serpentine in the repair agent is significantly increased after modification, which significantly reduces the charge transfer impedance in the gel electrolyte, and accelerates the decomposition of stable lead sulfate particles.

[0076] (2) The electrolyte with the added gel battery repair agent is stirred before filling, the stirring speed is 800r / min, the room temperature, and the direct filling method is used for battery filling, and the filling speed is 35mL / min. The inventor of the present application found that as the stirring speed increases, the distribution of the gel electrolyte becomes more uniform, so it is understandable that the cycle life of the battery prepared at a stirring speed of 800r / min is longer than that at a lower stirring speed. However, the cycle life at a stirring speed higher than 1200r / min is shorter than that at 800r / min, which may be because when the stirring speed is 1200r / min, the speed is too high, the gel molecules are destroyed under high speed stirring, the gel particles are dispersed, and the large particles gradually become small particles, and the small particles become smaller. These small particles are easy to precipitate water after gelation in the cycle process, which will affect the final cycle life, therefore, the stirring speed of 800r / min is a relatively appropriate choice.

[0077] The inventor of the present application has found through research that, at room temperature, the direct pouring method is better than high temperature or over-discharge method in terms of the uniformity of the distribution of the gel electrolyte and the longer cycle life. Although the initial capacity of the over-discharge method is larger, the capacity decays rapidly, and the discharge capacity is less than that of the direct pouring method from the 27th cycle to the end of the life. Therefore, the pouring method is selected as the direct pouring method at room temperature.

[0078] The inventor of the present application has found through research that, when the pouring speed is less than 30 mL / min, the initial discharge capacity of the gel battery increases as the pouring speed decreases. However, this is not conducive to industrial production. At the same time, a large amount of gas is generated when the gel electrolyte is poured into the battery tank. If the electrolyte is injected quickly, a large amount of electrolyte will block the gas discharge channel, making it difficult for the gas to be discharged, which will increase the internal resistance of the battery and reduce the discharge capacity. Therefore, the electrolyte should be injected at an appropriate speed to give the gas sufficient time and space to be discharged. Of course, the pouring speed cannot be too slow, which not only has a higher requirement for the gel time of the gel electrolyte, but also affects the speed of industrial production. Therefore, the pouring speed of 35 mL / min is a relatively appropriate speed.

[0079] (2) After the electrolyte is injected, the battery is first left to stand, and then the battery is subjected to charge and discharge activation; after the charge and discharge activation is completed, the battery is secondly left to stand, and is prepared for performance testing.

[0080] Two 12V 4AH transparent lead-acid batteries without liquid are taken, one of which is added with a repair liquid, and the other is not added with the repair liquid. The two batteries are subjected to cycle experiments under the same charge and discharge conditions to study the influence of the repair liquid on the cycle performance of the new battery.

[0081] 1) 46 mL of self-made sulfuric acid electrolyte is taken in a beaker, 2 mL of repair liquid is then added and stirred to mix uniformly, and the prepared mixed solution is added to a single cell of a transparent battery with a capacity of 4AH, and repeated to fill 6 single cells. Each cell is vacuumed for 60 minutes, and left to stand for 8 hours.

[0082] 2) 46 mL of self-made sulfuric acid electrolyte is taken into a single cell of a transparent battery with a capacity of 4AH, and repeated to fill 6 single cells. Each cell is vacuumed for 60 minutes, and left to stand for 8 hours.

[0083] 3) A microcomputer charge and discharge machine is used to perform charge and discharge cycle tests on the new battery

[0084] The new battery cycle charge and discharge process is set as follows:

[0085] 1. Charging: constant current charging at 0.1C, current is 0.4A, voltage upper limit is 15.6V;

[0086] 2. Discharge: constant current discharge at 5 hour rate, current is 0.8A, voltage lower limit is 10.5V;

[0087] 3. 27 charge-discharge cycles are performed on the battery, record the capacity change of the battery, and analyze.

[0088] The attenuation of new battery charge-discharge cycle is shown in Figure 3 It can be seen that the capacity of new battery without adding repair solution and new battery with adding repair solution both attenuate after 27 charge-discharge cycles, and the attenuation degree and speed of new battery with adding repair solution is obviously lower than that of new battery without adding repair solution. It shows that the repair solution in this paper has the effect of prolonging the service life of lead-acid battery.

Claims

1. A colloidal battery restorer, characterized by, Comprise: A repair powder prepared from natural magnesium-rich silicate ore, modified serpentine and 8-hydroxyquinoline; A mixture of nano-carbon particles, N-(2-hydroxyethyl) acrylamide, sodium sulfate and potassium sulfate; And deionized water; The natural magnesium-rich silicate ore, modified serpentine and 8-hydroxyquinoline are mixed in a mass ratio of 10:1:0.1, and the mixed material is placed in a high-temperature kettle, the temperature is set at 1500-1700℃, heated, cooled, and a repair powder is obtained; The nano-carbon particles, N-(2-hydroxyethyl) acrylamide, sodium sulfate and potassium sulfate are mixed in a ratio of 1:1:5:5 to obtain a mixture; The mixture is added to deionized water in a percentage of 0.01-0.03% of the mass of deionized water, and then 0.01-0.03% of the mass of deionized water of the repair powder is added, and mixed uniformly to obtain a colloidal battery repair agent; The preparation method of the modified serpentine is: S1: The natural serpentine is activated at high temperature, cooled, ground, sieved to obtain natural serpentine powder, stirred with water, then added with cysteamine hydrochloride for magnetic stirring, placed, washed with deionized water, and dried to obtain organic serpentine; wherein the mass ratio of natural serpentine powder to cysteamine hydrochloride is 100g:6g; S2: 0.1 mol·L-1 Na2CO3 solution was mixed with 0.1 mol·L-1 FeCl3·6H2O at a volume ratio of 1:2, and a polyhydroxy iron polymer solution was prepared by magnetic stirring, -1 -1 FeCl3·6H2O at a volume ratio of 1:2, and a polyhydroxy iron polymer solution was prepared by magnetic stirring,​ S3: 500 g·L of organic serpentine in deionized water was prepared by mixing the organic serpentine in S1 -1 The organic serpentine slurry was prepared by mixing the organic serpentine in S1 with deionized water, and then the polyhydroxy iron polymer solution in S2 was added, and the mixture was stirred by magnetic force, and then was washed to obtain modified serpentine. The volume ratio of the organic serpentine slurry to the polyhydroxy iron polymer solution was 3:

2.

2. The colloidal battery restorer of claim 1, wherein, The preparation method of the modified serpentine comprises one or more of the following i)-v) features, i) The natural serpentine is activated at a temperature of 400-600℃ for 40-60min; ii) The sieving is 100-150 mesh; iii) The magnetic stirring time in step S1 is 1-2h, and the magnetic stirring time in step S3 is 1-2h; iv) The drying temperature in step S1 is 60-70℃; v) The mixture of natural magnesium-rich silicate ore, modified serpentine and 8-hydroxyquinoline is heated in a high-temperature kettle for 0.5-2 hours.

3. The colloidal battery restorer of claim 1, wherein, The nano-carbon particles have a particle size of ≤50 nm and a resistivity of ≤5×10 -4 Ω.cm.

4. A method of using a colloidal battery restorer, characterized by, Comprise the following steps: (1) The colloidal battery repair agent of any one of claims 1 to 3 is first added to the electrolyte, and the electrolyte with the colloidal battery repair agent is stirred before filling, the stirring speed is 800r / min-1200r / min, the room temperature, and the battery is filled by direct filling method, the filling speed is 30-45mL / min; (2) After the electrolyte is injected, the battery is first placed, and then the battery is charged and discharged for activation; after the charging and discharging activation is completed, the battery is secondly placed, and the performance test is prepared.

5. The method of using a colloidal battery restorer of claim 4, wherein, The stirring time is 15-25min, and the first and second battery standing times are both 5-24 hours.

6. A method of using a colloidal battery restorer, characterized by, The colloidal battery repair agent of any one of claims 1 to 3 is heated to 75-85℃, and the colloidal battery electrolyte is added into the colloidal battery from the valve port of the colloidal battery by direct filling method, and then the battery is charged and discharged for activation, and after the charging and discharging activation is completed, the battery is secondly placed, and the performance test is prepared.

7. The method of using a colloidal battery restorer of claim 6, wherein, The amount of colloidal battery repair agent added is 0.5ml per colloidal battery surface capacity AH.

8. The method of using a colloidal battery restorer of claim 6, wherein, The charging and discharging activation is a charging and discharging cycle process, the charging voltage is less than 2.85V, and the charging current is 0.02C-0.2C, which is a charging state; the charging voltage is greater than or equal to 2.85V, or the charging current is less than 0.02C, which is a discharging state.

9. The method of using a colloidal battery restorer of claim 8, wherein, The charging and discharging cycle process is repeated at most 2 times.

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