TWI231617B - Liquid low-sodium silicate forming-solution used for a storage battery, and a container formation method - Google Patents

Abstract

The present invention relates to a liquid low sodium silicate forming solution used for storage batteries and a container formation method. Such a forming solution is prepared by mixing 5 to 15 weight units of silica gel containing 40 to 60 wt% SiO2 with 15 to 25 weight units of water, adjusting the pH value of the mixture to 1-4 using inorganic acid and magnetizing the mixture in 1000 to 6000 Gauss magnetic field for 5 to 10 minutes, and finally obtaining a liquid low sodium silicate forming solution having a viscosity smaller than 0.02 poise; filling the forming solution into a battery tank and using a charger to activate electrochemically. The operating temperature is room temperature and time is 30 to 50 hours. Using such a forming solution and procedures described above can avoid the releasing of acid smog and serious environmental pollution and healthy hazard for workers. Attributed to liquid state and good fluidity of the activation solution and not producing heat during activation, the battery as made can be activated within a short time and the rate performance can be improved to 25 to 30C.

Description

1231617 _ Case No. 92132483_ Year 5. Description of the invention (1) Revision [Technical field to which the invention belongs] The present invention is a process technology of liquid low-sodium sulphate salinization liquid, especially the liquid low-sodium for battery Shixi salinization liquid and method. [Prior art]

The liquid low-sodium salt sulfide formation of the battery is an indispensable t-process in the manufacture of the battery industry. The formation process is generally an unformed electrode plate. The electrode plate is converted into The formation of the paste on the electrode plate turns into an active material, U Pb02 and / 3 -Pb02 are formed on the positive electrode, and sponge-like metal lead is formed on the negative electrode. This process is called chemical conversion. Battery plate formation is generally divided into two methods: t a n k formation (external formation) and battery box formation (container format ion) (internal formation). The tank formation method involves immersing a cured plate in a formation tank and using a sulfuric acid solution having a specific gravity of 1.03 to 1.15 to form a current through electrolysis. However, the battery formation method is to divide the mature plate saw into small pieces, assemble the plate group, put it into the battery case, seal the cover, and then add a sulfuric acid solution with a specific gravity of 1 · 0 3 ~ 1 · 30, and power on. Into.

Regardless of the formation method, it is a formation solution prepared with water and sulfuric acid (a formation solution containing sulfuric acid solution as the main component). In the formation process, it includes welding and immersion technology, electrification formation technology, etc. A large amount of acid mist generated when the ratio S04 is mixed with water not only causes serious pollution to the environment, but also causes great harm to the operator. In addition, the chemical conversion method using H2S04 and water is used for the formation method. Because the high heat generated when JJ2SQ4 is combined with water, the conventional synthetic technology steps are complicated, the operation is labor-intensive, and the conventional H2S04 conversion liquid is converted into Long time, resulting in polarization

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Insufficient performance often results in the disadvantage of small battery capacity. [Summary of the invention] ^ The purpose of the present invention is to overcome the shortcomings of the existing sulfuric acid solution as the main component and the water composition solution, in order to completely solve the acid mist escape during the formation process to pollute the environment and endanger workers, creating for battery technology A safe working environment; in order to shorten the formation time, achieve full formation, and increase battery capacity; at the same time, reduce the formation process and reduce the labor intensity of operators, and provide a liquid low-sodium silicon salt formation solution and internalization method for batteries The invention uses the stability of liquid low-sodium silicon salt formation liquid to be more stable than the conventional flowing acid solution, and can solve the disadvantage of generating a large amount of acid mist during the conventional formation process. In addition, the low-sodium silicon salt formation liquid of the present invention is a liquid formation liquid. The liquid formation liquid has good fluidity, does not generate heat during formation, and can be charged and differentiated in the shortest time, greatly improving the battery capacity. In addition, the present invention is an internal chemical conversion technology, such as the conventional internal chemical conversion technology. This chemical conversion method has the advantages of lightening labor processes compared with tank chemical conversion (external chemical conversion) and shortening the chemical conversion time. [Embodiment] The purpose of the present invention is to realize the present invention. The present invention provides a method for producing a liquid low-sodium silicon salting liquid used in a storage battery. The liquid low-sodium stone salting liquid uses magnetization technology. Obtained: 1. Obtain 5 to 15 parts by weight of Shi Xisol of 40 ~ 60 wt% Si 02. 2. Add water to the sol in step 1 while mixing, add 15 to 25 parts by weight of water, and insert the mixture with a Pommel's hydrometer to measure the concentration of Pomex. When the concentration of Pomex is 0.65 ~ When 0.85% Be ', no more water is added.

Page 5 1231617: First Amendment 5 Case No. 92132 ^ 1 Description of the Invention (3) The water system is deionized water or distilled water. 3. Adjust the value of the mixture with an inorganic acid, add the inorganic acid to f, mix it, and add the inorganic acid while measuring the amount of the two: The acids include: hydrochloric acid, oxalic acid, and sulfuric acid. The above-mentioned inorganic 1 nnn ^ f ~ the mixture obtained in step 3 above is put into a magnetic field with a magnetic field strength of ~ 60,000 鬲 s, and the magnetization is performed for 5 to 10 minutes; 苴 22, the magnetic field is a magnetic material Produced drums, or AC, DC magnetic

%, The above-mentioned magnetic materials include ferro-boron magnets, iron nutrients, and other magnetic materials. Inch and its 5. Stirring the magnetized mixture in step 4 above, its stirring bag ^ artificial stirring or mechanical mixing, its mechanical mixing speed is 7qq ~ H00 rpm / minute 'mixing for 5 ~ 10 minutes, making step 4 The resulting mixture has a reduced viscosity. When the viscosity was less than 0 · 〇2 poise (mpas), the stirring was stopped with a square-rotor viscometer, and the liquid low-sodium salicylate liquid used for the storage battery with a viscosity less than 0 · 02 poise was obtained. The liquid low-sodium silicon salt formation liquid used in the storage battery provided by the present invention includes a formation liquid that can be used in ordinary storage batteries or special storage batteries, such as deep-sea storage batteries. The method for internalizing a battery using the liquid low-sodium silicon salting solution of the present invention includes the following steps: mm ° 1. · First make a plate peach: a hexagonal honeycomb mesh grid made of the wrong or wrong alloy, the size is just right It is advisable to pack it into the case of a box-type battery. The thickness of the positive and negative grids is the same as conventional, except that the frame of the negative grid is thicker than the honeycomb part inside the frame. 0.2 to 0. 6 mm 3,0. 8 1231617 _ Case No. 92132483_ £ 5. The description of the invention (4) Revision 2 · The electrode plate is coated with lead paste: the electrode plate of the present invention The applied lead paste is not the same as the lead paste or lead paste applied on the ordinary lead battery electrode plates, in which the positive electrode plate of the present invention is coated with poor or poor lead. 100 kg of lead powder, 500 g of graphite, and short-fiber paper 50 g, sulfuric acid 12.26 kg (25 ° C d = 1.38), and 14 kg of water are mixed. The density of the lead paste is 4.2 g / cm3, and the prepared lead paste is coated by the usual method. On the positive electrode plate, wherein the lead paste coated on the negative electrode plate of the present invention is: lead powder i.00 kg, barium sulfate 500 g, staple fiber paper 50 g Sulfuric acid 8.19 kg (25 ° C = 1. 3 8) and 14 kg of water are mixed. The density of the lead paste is 4.3 g / αη3, and the prepared paste is coated on the negative plate by the usual method. on. The water mentioned therein includes distilled water and deionized water. The positive and negative grids coated with the wrong paste prepared by Zhaibing U f Step 2 were placed on the eight f: 2 'battery wall uniformly arranged in the plastic case of the battery. One grid (slot) design, one negative and one positive grid are placed close to each other in each grid, and $,. ^ ^ ^ Μ is placed between the positive and negative grids with a barrier cotton between the two adjacent boards. Leave the ears on the prepared grid in two: two and i are arranged in a per-grid ^ each-species ^ IS ift ^ X ^ Λ 汇 The positive and negative grids in a grid are each with a sink / knife L plate 逋The plate lugs are connected in parallel, so the connecting posts are connected in series, and then the positive and negative grids are connected to the positive and negative poles, and the grids and poles are behind them. The cover of the battery case is usually installed in the same way; however, there must be no ventilation between the cells. Seal each cell with epoxy resin. 4. Move the prepared battery ^ and move the battery tank to remove the entire lightning point. When adding the chemical solution in the tank, the speed will be within 1 place. Air bubbles, letting the entire battery case

Chemical solution is injected into each cell in the tank. Liquid low-sodium silicon salt for storage batteries supplied by neodymium 1231617 ____Case No. 92132483_ year__day_revision____ V. Description of the invention (5) The space is filled with chemical solution; The rest of the plate outside the ears are soaked in the chemical solution, soaked for 12 to 24 hours, so that the chemical solution penetrates the electrode plate and the spacer, so that it does not generate heat during the chemical formation and achieves complete chemical conversion. 5. Use a formation charger to conduct electricity formation. Use "uc — KGCFD2 microcomputer battery formation discharge power source" or "uc — KGCFD 2 economical 40 loop charge and discharge power source" to form and power up the battery installed in step 4. Temperature: room

Temperature; formation time: 30-50 hours, 48 hours optimized formation voltage is 2.2V 〇 The liquid low-sodium stone salt formation liquid used in the storage battery of the present invention and the internal formation method can obtain the following effects and advantages: 1 · The liquid low-sodium silicon salt formation liquid used in the storage battery provided by the present invention completely solves the escape of a large amount of acid mist generated during the formation of the storage battery to avoid serious pollution to the environment and cause great harm to the operator. Therefore, Social benefits are particularly significant. 2 · The liquid low-sodium silicon salt formation liquid used in the present invention is a liquid formation liquid, which overcomes the existing problems of colloid formation liquid formation. The liquid formation liquid has good fluidity, does not generate heat during formation, and can reach Fully formed in the shortest time. 3. The present invention adopts self-made positive and negative grid lead paste and the thickness of the positive and negative grid is inconsistent ', especially the thickness of the grid frame is thicker than the middle part, so that more lead paste can be coated on the positive and negative grid peaches, and the effective activity is greatly increased. Materials, because according to Faraday's second law, a certain amount of effective active material must be consumed when the battery is discharged, the discharge capacity of the battery prepared by using the liquid low-sodium silicon salt formation liquid and the formation method of the present invention is increased to a discharge capacity of 25C ~ 30C.

Page 81231617-Wei 92] Milk class __ year and month ___ 5. Description of the invention (6) 4 · The liquid low-sodium silicon salification liquid prepared by the present invention is also the electrolyte of the battery, and simplified by internal chemical conversion technology The formation process has been reduced, the labor burden of the operator has been reduced, the formation time has been shortened, and the work efficiency has been improved. 5 · When the liquid low-sodium stone is used for salinization and liquefaction, the battery tank is soaked for a long time, and the battery tank is evenly shaken when the chemical is added. , When the electricity is formed, the formation is complete, and it will not generate heat during the use of the battery, which greatly increases the capacity of the battery. Task 6 · The service life of the battery prepared by using the liquid low-sodium silicon salt chemical conversion liquid of the present invention is increased to more than 1,000 times. The battery can be used normally at a temperature of -50 ° C ~ + 60 C, and it starts. The capacity is greatly improved, and the general 3-7C discharge capacity is increased to 25C ~ 30C discharge capacity. The battery has small electrodes. The long-term storage period can be used normally up to 18 months. The energy can reach more than 53w / kg. The chemical conversion curve of the liquid low-sodium silicon salt chemical conversion liquid of the present invention is as shown in [Figure 1]. Embodiments of the present invention: Example 1: ^ Prepare the present invention for liquid low-sodium silicates for 12n2 ampere-hour batteries • Use commercially available reagents (commercial model: Model S-40) containing 40WT% 1 5 parts by weight of the silicon solution of 2 was actually taken 5 kg of the silica sol. j Take 15 liters of distilled water and add it to the above silica sol, while adding distilled water to the basket μ ′, measure the solution ’s concentration with a specific gravity meter ’, and the value displayed on the specific gravity meter is 0.65%. β e, so far, no more steam

1231617 _ Case No. 92132483_ Year Month __ ^ _ V. Description of the invention (7) 3. Add the commercially available 98.3% H2S04 to the mixture obtained in the above step 2 while adding H2 S 04 with an acidity meter. Measure its P Η value to 1 · 5 7 and stop adding 'that is, add 2 liters of H2S04. 4. Put the mixture obtained in step 3 above in a circular barrel with a diameter of 800 mm and a barrel height of 800 mm made of a magnet with a side iron. It has a magnetic field strength of 4 00 Gauss. Put it in the center of the magnetic field_ line 8 minutes for magnetization 5 · Mechanically stir the magnetized mixture in step 4 above. The mixing speed is 7 0 ~ 1 4 0 0 rpm, stir for 6 minutes, and measure with a rotary dryness meter. The viscosity was reduced to less than 0.002 poise (mPas) to prepare a liquid low-sodium silicate conversion solution for a KV12 ampere-hour lead storage battery. Example 2: The liquid low-sodium silicate chemical conversion solution prepared in Example 1 was used for internalization. The steps are as follows: (1) First, the grid of the electrode plate is made of a hexagonal honeycomb mesh with a wrong or wrong alloy. The grid is sized to fit into the case of the trough battery. The thickness of the positive and negative grids is the same as that of the conventional ones, except that the frame of the negative grid is thicker than the honeycomb mesh part in the frame. 0.6 mm, the frame of the front grid is thicker than the honeycomb part within the frame 0.8. (2) The positive electrode lead paste of the present invention is applied to the positive electrode grid by a common method. The positive electrode grid wrong paste is composed of 100 kg of ship powder, 5000 g of graphite, 50 g of staple fiber paper, and sulfuric acid 12. 26 kg (25t buckle 138), water "kg mixed, the density of the lead paste is 4.2 g / cm3. (, 3) Place the unformed grid coated with lead paste obtained in step 2_1 In the plastic case of the battery, there are 6 cells in the battery case according to the design of the battery every 2 volts

Page 10 1231617 Amendment No. 92132481 V. Description of the invention (8) The doors are separated by partition walls, each cell has a z-, positive grid-phase phase grid if, and a positive-, negative-gate grid is placed in the middle. Cotton, there are no gaps between the two adjacent plates, and they are arranged in each grid. A total of 6 grids, 10 cotton spacers, and 5 positive grids are placed; the ears on each grid are the same. -The lugs on the positive and negative grids in the grid are connected in parallel by bus plates, respectively. The positive and negative grids between the grid and the grid are connected in series through the connection posts, and t ^ is connected to the positive and negative posts; then The battery case is covered with a cover, and each cell is sealed with epoxy resin, and there is no ventilation between the cells. (_4) Inject the liquid low-sodium silicon salinization solution prepared in Example χ into each cell in the tank, place the assembled battery on a vibration machine with constant speed, and shake while adding the chemical solution into the battery tank. In order to remove air bubbles, fill the entire space with liquid low-sodium silicon salt formation liquid, and soak the entire part except the plate ears in the heart formation fluid, soak for 20 hours, so that the formation fluid penetrates the electrode plate and Isolation cotton, so as not to generate heat during the formation process, to reach the end of the formation. (5) Use a formation charger to conduct electrification and use, for example, "uc_KGCFD2 microcomputer battery formation discharge power source", and turn the battery on and form at room temperature; formation time: 48 hours. Optimized formation voltage 2.2V. 12V12Ah in this embodiment The internal formation curve of the wrong battery is shown in "Figure 2." The chemical conversion solution prepared in this example 1 is used to form the chemical conversion solution, and the chemical conversion solution serves as the battery electrolyte. The lead storage battery standard is 丨 〇〇; lead storage battery The specific energy reaches more than 53W / kg; the service life is increased to more than 1,000 times; the battery can be used normally at a temperature of _50C ~ + 60C; the starting capacity is improved, from the general 3 ~ 7C discharge capacity to 25C ~ Discharge capacity above 30C. The battery has a small self-discharge electrode and can be stored for a long period of time up to 8 months. 1231617

-Case No. 92132483 V. Description of Invention (9) Use. Example 3: The chemical conversion solution and chemical conversion method of this example are the same as those in Examples XI and 2 except that: °° The commercially available reagent used to prepare the chemical conversion solution is a silica sol containing 60 wt% s 丨 〇2. 85%。 5 kg; deionized water was added 20 liters, when the concentration of pomegranate of the mixture was 0.85%. Be, when no more water is added, then add sulfuric acid to the mixture, measure the pH of the mixture while adding sulfuric acid, stop adding ^ until the pH value is 4, place the mixture in the mixture with a magnetic field strength of Magnetization was performed in a magnetic field of 6000 faces for 6 minutes. The difference in the formation method is that the frame of the negative grid is 0.3 (mm) thicker than the mesh part of the nest in the frame, and the frame of the positive grid is 0.5 (mm) thicker than the honeycomb part in the frame. Soak for 12 hours; use uc_KGCFD2 economical 40 circuit charge / discharge power supply " power on the battery to form, form temperature and room temperature; formation time: 35 hours; formation voltage 2.2V. Example 4: The chemical conversion solution and the chemical conversion method prepared in this example are the same as those in Examples 1 and 2 except that the commercially available reagent used to prepare the chemical conversion solution is a pure silica sol containing 60% by weight of Si02. 15 parts by weight; adding deionized water to support parts by weight 'measured its Pomeranian concentration to be 0.85%. Be, no more water is added; add oxalic acid to the mixture, measure the pH of the mixture while adding oxalic acid, stop adding water until the pH value is 3, and place the mixture in a direct current with a magnetic field strength of 6000 faces Magnetize in a magnetic field for 6 minutes; the difference between the methods of formation is that the frame of the grid is more than the honeycomb mesh portion of the frame " 1231617 _Case No. 92132483_ Year Month Revision _5. Description of the invention (10) Soaking in liquid 1 2 hours; fl UC-KGCFD2 economical 40 circuit charge / discharge power source π is applied to the battery, and the formation temperature is room temperature; the formation time: 50 hours; the formation voltage is 2.07 V. However, the above are only preferred embodiments of the present invention and are not intended to limit the scope of implementation of the present invention. That is to say, all equivalent changes and modifications made according to the scope of patent application of the present invention are covered by the scope of patent of the present invention.

Page 1312316 Case No. 92132483 Revised diagrams Brief description of the first diagram, the lead battery is formed by the liquid low-sodium silicon salt formation liquid of the present invention, and the second diagram is a 12V12AH lead battery of the present invention. Implementation curve

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Claims (1)

No. 1231617 92132483 6. Scope of patent application 1 · Preparation and removal of a liquid low-sodium silicon salification liquid used in a storage battery. The liquid low-sodium silicon salification liquid is prepared by magnetizing technology according to the following steps (1) 5 to 15 parts by weight of silica sol of ~ 6 Owt% Si 〇2; and (2) adding 15 to 25 parts by weight of water to mix, add water to the silica sol in step (1) while stirring, when the Baume concentration It is 0.65 to 085%. B. No more water. (3) Add the inorganic acid to the product obtained in the above step (2) and mix it: measure the pH value of the mixture while adding the inorganic acid until the pH value stops adding the inorganic acid to obtain silicic acid. Salt mixture;… (4) Mix the silicate in step (3) above. The magnetization is performed in a Gauss magnetic field, and the magnetization time is: divided into the silicate mixture after the magnetization is known;-the knife (5) magnetizes the mixture after the step (4), and the mixture viscosity is less than 0. 〇2 stop stirring, #, + Tian low sodium silicate into a liquid. Liquid state for animal battery 2. The water system described in item 1 of the scope of patent application is deionized water or steamed water. I operation method 'wherein the inorganic acid prepared as described in item 丨 of the scope of application for patent includes hydrochloric acid, oxalic acid, and sulfuric acid. This method, where '4. As mentioned in item 1 of the scope of the patent application, the mixing speed is 700 ~ 140 rpm / min ^ method, where +5 is as described in the scope of the patent application The system \ 5 ~ 10 minutes. The magnetic field described includes a method using ytterbium-iron-boron magnetism, in which all iron 1 ^ is made—one with 1 000 ~ 6000. Page 15 1231617 Λ ___ Ά Amendment No. 92132483 6. Application scope of patent Gaussian circular barrel magnetic field. 6 · An internalization method using a liquid low-sodium silicon salinization liquid used in a storage battery prepared as described in item 1 of the scope of the patent application, the internalization method includes the following steps: (1) first making a grid of an electrode plate · · Lead or lead alloy made of hexagonal honeycomb mesh grid, it is suitable to fit into the casing of the box battery. The thickness of the positive and negative grids is the same as that of the conventional ones, except that the difference lies in the negative grid. 3 ~ 0. 8 mm; (2) the positive plate is coated with Lead paste: The positive electrode plate is coated with lead powder, 0.00 kg, graphite, 500 g, staple fiber paper, 50 g, sulfuric acid, 1.2, 2 and 6 kg (25 ° C d = 1 · 3 8), water 14 kg of mixed lead paste, the density of the lead paste is 4.2 g / cm3; the lead paste coated on the negative plate is 100 kg of lead powder, 5000 g of barium sulfate, 50 g of staple fiber paper, Sulfuric acid 8.19 kg, water 14 kg, mixed with lead paste density of 4.3 g / cm3; (3) Unformed electrode plate is placed in the battery case, the battery case is uniform The partition wall is divided into several compartments. The design is based on a grid of 2 volts. A negative and a positive grid are placed close to each other in each grid. An insulating cotton is placed between the positive and negative grids. There are no gaps between the grids, and they are arranged in each grid. The ears on the female grid are on the same side. The positive and negative grids in the same grid are connected in parallel by the bus bars through the ears. The positive and negative grids between the grids are connected in series by connecting posts, and then connected to the positive and negative poles. The grid, poles, and connecting posts are connected in the same way as ordinary battery installations; Cover the shell with an epoxy resin seal Page 16 1231617 -92132483 May 6th, application for application 15 '"' ----- Seal each card, there should be no ventilation between the cells; (4,) the prepared invention provided The battery is filled with liquid low-sodium silicon salification liquid into each cell in the tank, and the rest except the plate ears are soaked in the formation liquid and soaked for 12 to 24 hours; (5) using a formation charger to conduct electricity formation; The formation temperature is room temperature; the formation time is 30 to 50 hours. 7. The internalization method as described in item 6 of the scope of the patent application, wherein the formation charger uses a uc-KGCFD2 microcomputer battery to form a discharge power source or a UC-KGCFD2 economical 40-circuit charge-discharge power source to form a battery. 8 · The internalization method as described in item 6 of the scope of patent application, wherein the optimization time is 48 hours, and the optimization voltage is 2 · 〇7 ~ 2 · 6 V