Detection method for analyzing corroded grid components in battery and auxiliary equipment

Abstract

The invention relates to a detection method and auxiliary equipment for analyzing components of a corroded grid in a battery. The detection method comprises the following steps: preparing a sample; testing the sample by using a direct-reading spectrometer, and recording data; wherein the step of preparing the sample comprises the following steps: taking a battery inner grid; the grid is treated with a cleaning solution, then cleaned with pure water and aired, and the cleaning solution has reducibility and can dissolve residues on the surface of the grid, so that the metal color of the grid is exposed; and embedding the air-dried grid or a part of the structure thereof in pure lead to serve as a sample. The detection method can avoid the interference of impurity elements in the corrosion layer and the battery, and the detection result is accurate.

Description

Technical Field

[0001] The present invention relates to the technical field of batteries, and in particular to a detection method and auxiliary equipment for analyzing the components of corroded grids in batteries. Background Art

[0002] Lead-acid batteries are widely used in power grid energy storage, telecommunications, transportation and other fields due to their mature technology, low cost, safety, reliability and high material recovery rate.

[0003] There are many reasons for the failure of lead-acid batteries, such as sulfation, water loss, thermal runaway, active material shedding, plate softening, etc. For batteries with abnormal failure or long cycle life, the battery is usually dissected to find out the reasons for failure and long cycle life.

[0004] The grid is the main component of the lead-acid battery. It is the collector skeleton of the electrode. It conducts, collects and distributes the current evenly. It also supports the active material and is the carrier of the active material. The corrosion problem of the positive grid of the lead-acid battery seriously restricts its service life. The composition of the grid alloy has a great influence on the battery. The appropriate composition can ensure that the grid has good mechanical strength. For example, adding some calcium to the alloy can make it less likely to deform and damage during the assembly and use of the battery, thereby maintaining the integrity of the battery structure. Different compositions will also lead to differences in the corrosion resistance of the grid. A grid with good corrosion resistance can extend the service life of the battery and reduce the degradation of battery performance caused by grid corrosion. The appropriate composition can also reduce the oxygen evolution of the positive electrode and the hydrogen evolution of the negative electrode of the battery, reduce the water loss of the battery, and increase the battery life. Lead-calcium alloy has been widely used in maintenance-free lead-acid batteries because of its advantages such as high hydrogen evolution overpotential and low water loss. When looking for the cause of battery failure, people will also collect the battery grid for component analysis.

[0005] During the charging and discharging process of lead-acid batteries, the high battery temperature and the corrosive acids or organic salts contained in the electrolyte will cause significant corrosion of the positive electrode grid, making it impossible to obtain the grid composition in its initial state. Summary of the invention

[0006] Based on this, it is necessary to provide a detection method and auxiliary equipment for analyzing the components of corroded grids in batteries in response to the above-mentioned technical problems existing in the prior art. The detection method of the present invention can avoid the interference of corrosion layers and impurity elements in batteries, and the detection results are accurate.

[0007] In order to solve the above technical problems, the technical solution adopted by the present invention is:

[0008] A method for analyzing the components of corroded grids in a battery comprises the following steps:

[0009] Prepare the test specimen;

[0010] Test the sample with a direct reading spectrometer and record the data;

[0011] The preparation of the sample includes:

[0012] Take a battery inner grid;

[0013] Treat the grid with cleaning liquid, then wash it with pure water and dry it. The cleaning liquid has reducing properties and can dissolve the residue on the surface of the grid, revealing the metal color of the grid.

[0014] Take the dried grid or part of its structure and embed it in pure lead as a sample.

[0015] In a feasible implementation, the cleaning liquid is a sugar alkali solution, and the mass percentage of sugar alkali in the sugar alkali solution is 10%-40%, specifically, it can also be 10%-35%, 15%-35%, 15%-30%, more specifically, it can be 15%, 20%, 25%, 30%;

[0016] Preferably, the mass ratio of sugar to alkali in the sugar alkali solution is 3.0:1-4.3:1, specifically, it can also be 3.0:1-4.0:1, 3.2:1-4.0:1, 3.5:1-4.0:1;

[0017] Preferably, the sugar in the sugar-alkali solution is glucose and the alkali is sodium hydroxide;

[0018] Preferably, the cleaning liquid treatment is carried out under heating conditions, and the heating temperature is 85-105°C, specifically, it can also be 90-105°C, 90-100°C, 95-100°C;

[0019] Preferably, a partial structure of the grid is a tab of the grid.

[0020] In a feasible implementation, the specific operation of testing the sample with a direct reading spectrometer is to select the lead-based general analysis procedure Pb-01, select a standard sample to calibrate the equipment, and then excite the sample, excite the same sample at least twice, and record the data;

[0021] Preferably, the direct reading spectrometer has the ability to detect elements such as Ca, Sn, Al, Ag, Cu, Bi, S, Te, Mg, and Pb.

[0022] The analysis spectra and detection limits of each element are as follows:

[0023] Ca: 315.887nm, 0.00020%-1.3%

[0024] Sn: 317.505nm, 0.00010%-1.3%

[0025] Al: 309.271nm, 0.000010%-0.0750%

[0026] Ag: 338.289nm, 0.000050%-0.0250%

[0027] Cu: 324.753nm, 0.00001%-0.0150%

[0028] Bi: 306.772nm, 0.000050%-1.2%

[0029] S: 180.731nm, 0.00010%-0.0110%

[0030] Te: 214.28nm, 0.00010%-0.100%

[0031] Mg: 279.077nm, 0.000050%-0.180%.

[0032] The detection method of the present invention can avoid the interference of impurity elements in the corrosion layer and the battery, and the detection result is accurate.

[0033] A method for analyzing the components of corroded grids in a battery comprises the following steps:

[0034] Prepare the test specimen;

[0035] Test the sample with a direct reading spectrometer and record the data;

[0036] The preparation of the sample includes:

[0037] Take a battery inner grid;

[0038] Take a part of the grid structure and treat it with a cleaning solution, then wash it with pure water and dry it. The cleaning solution has a reducing property and can dissolve the residue on the surface of the part of the grid structure, so that the part of the grid structure reveals its metallic color;

[0039] Take part of the grid structure after drying and embed it in pure lead as a sample.

[0040] In a feasible implementation, the cleaning liquid is a sugar alkali solution, and the mass percentage of sugar alkali in the sugar alkali solution is 10%-40%, specifically, it can also be 10%-35%, 15%-35%, 15%-30%, more specifically, it can be 15%, 20%, 25%, 30%;

[0041] Preferably, the mass ratio of sugar to alkali in the sugar alkali solution is 3.0:1-4.3:1, specifically, it can also be 3.0:1-4.0:1, 3.2:1-4.0:1, 3.5:1-4.0:1;

[0042] Preferably, the sugar in the sugar-alkali solution is glucose and the alkali is sodium hydroxide;

[0043] Preferably, the cleaning liquid treatment is carried out under heating conditions, and the heating temperature is 85-105°C, specifically, it can also be 90-105°C, 90-100°C, 95-100°C;

[0044] Preferably, a partial structure of the grid is a tab of the grid.

[0045] The present invention uses sugar-alkali solution to treat the grid, and the treatment effect is good.

[0046] In a feasible implementation, the direct reading spectrometer is used to test the sample. The specific operation of the direct reading spectrometer parameter setting is to select the lead-based general analysis program Pb-01, select the standard sample to calibrate the equipment, and then excite the sample. The same sample is excited at least twice, and the data is recorded;

[0047] Preferably, the direct reading spectrometer has the ability to detect elements such as Ca, Sn, Al, Ag, Cu, Bi, S, Te, Mg, and Pb.

[0048] The analysis spectra and detection limits of each element are as follows:

[0049] Ca: 315.887nm, 0.00020%-1.3%

[0050] Sn: 317.505nm, 0.00010%-1.3%

[0051] Al: 309.271nm, 0.000010%-0.0750%

[0052] Ag: 338.289nm, 0.000050%-0.0250%

[0053] Cu: 324.753nm, 0.00001%-0.0150%

[0054] Bi: 306.772nm, 0.000050%-1.2%

[0055] S: 180.731nm, 0.00010%-0.0110%

[0056] Te: 214.28nm, 0.00010%-0.100%

[0057] Mg: 279.077nm, 0.000050%-0.180%.

[0058] Compared with the detection methods of inductively coupled plasma spectrometer (ICP) and atomic absorption spectrophotometer, the detection method of the present invention reduces the weighing and digestion processes, saves detection time, and can detect the contents of multiple elements at the same time.

[0059] In order to solve the above technical problems, another technical solution adopted by the present invention is:

[0060] An auxiliary device for the detection method as described above is used to analyze the components of corroded grids in batteries, including a box, a lifting basket, and a driving mechanism. The box is used to place cleaning liquid, the lifting basket is arranged in the box and can move up and down relative to the box, the grid or part of its structure is placed in the lifting basket, and the driving mechanism is used to drive the lifting basket to move.

[0061] The auxiliary equipment of the present invention is used for cleaning the grid, and is convenient for observing the cleaning status of the grid at any time, thereby solving the problem in the prior art that it is impossible to confirm whether the grid is cleaned due to the color change of the cleaning liquid.

[0062] In a feasible implementation, a heating device is provided in the box to heat the cleaning liquid.

[0063] In a feasible implementation, a stirring device is provided in the box to stir the cleaning liquid;

[0064] Preferably, the stirring device is arranged at the bottom center of the box body;

[0065] Preferably, a partial structure of the grid is a tab of the grid.

[0066] The invention can ensure that the temperature of the liquid in the box is uniform, and prevent the sugar-alkali solution from suddenly boiling over and overflowing to injure people.

[0067] In a feasible implementation, the bottom of the lifting basket is provided with a through hole, and the number of the through holes is multiple;

[0068] Preferably, the area of ​​the plurality of through holes is greater than or equal to 1 / 3 of the bottom area of ​​the lifting basket, and less than or equal to 2 / 3 of the bottom area of ​​the lifting basket.

[0069] The present invention provides through holes to ensure that the state of the grid can be observed more clearly when the lifting basket is raised. At the same time, the limitation of the through hole area ensures the strength of the lifting basket on the one hand, and the descending speed of the sugar-alkali solution on the other hand, which is convenient for observation and saves time.

[0070] Preferably, a partition plate is provided inside the lifting basket, and the partition plate divides the interior of the lifting basket into at least two storage spaces;

[0071] Preferably, the partition plate is provided with a plurality of connection holes, and adjacent storage spaces are connected through the connection holes;

[0072] Preferably, the side wall of the lifting basket is configured as a transparent plate;

[0073] Preferably, the area of ​​the multiple connection holes provided on the partition plate accounts for 1 / 3-2 / 3 of the area of ​​the partition plate.

[0074] The present invention is provided with multiple storage spaces, and multiple plate grid ears can be cleaned at the same time to improve efficiency. The limitation of the connection holes ensures the strength of the lifting basket on the one hand, and facilitates the descending of the sugar-alkali solution when the lifting basket is raised on the other hand, so as to facilitate the observation of the cleaning degree of the pole ears. At the same time, the side wall of the lifting basket is provided with a transparent plate to facilitate the observation of the cleaning degree of the internal pole ears.

[0075] In a feasible implementation, a drainage device is provided at the bottom of the box.

[0076] Due to the adoption of the above technical solution, the present invention has the following advantages compared with the prior art:

[0077] 1. The detection method of the present invention can avoid the interference of impurity elements in the corrosion layer and the battery, and the detection result is accurate;

[0078] 2. Compared with the detection methods of inductively coupled plasma spectrometer (ICP) and atomic absorption spectrophotometer, the detection method of the present invention reduces the weighing and digestion processes, saves detection time, and can detect the contents of multiple elements at the same time.

[0079] 3. The auxiliary equipment of the present invention is used for cleaning the grid, which is convenient for observing the cleaning status of the grid at any time, and solves the problem in the prior art that it is impossible to confirm whether the grid is clean due to the color change of the cleaning liquid;

[0080] 4. The auxiliary equipment of the present invention is provided with a stirring device, which can ensure that the temperature of the liquid in the equipment is uniform and prevent the cleaning liquid from suddenly boiling and overflowing to injure people. BRIEF DESCRIPTION OF THE DRAWINGS

[0081] Figure 1 This is a physical picture of the electrode plate in Example 1;

[0082] Figure 2 This is a physical picture of the grid after the surfactant is removed in Example 1;

[0083] Figure 3 This is a physical picture of the grid after being treated with sugar-alkali solution in Example 1;

[0084] Figure 4 It is a structural schematic diagram of the auxiliary equipment of the present invention;

[0085] Figure 5It is a structural schematic diagram of a box body of the auxiliary equipment of the present invention;

[0086] Figure 6 It is a structural schematic diagram of the lifting basket of the auxiliary equipment of the present invention.

[0087] Among them, 1. box body; 11. support column; 2. lifting basket; 21. through hole; 22. storage space; 23. connecting hole; 24. partition plate; 3. heating device; 4. stirring device; 5. drainage device. DETAILED DESCRIPTION

[0088] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific embodiments of the present invention are described in detail below in conjunction with the accompanying drawings. In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without violating the connotation of the present invention, so the present invention is not limited by the specific embodiments disclosed below.

[0089] It should be noted that when an element is referred to as being "fixed to" another element, it may be directly on the other element or there may be a central element. When an element is considered to be "connected to" another element, it may be directly connected to the other element or there may be a central element at the same time. The terms "vertical", "horizontal", "left", "right", "upper", "lower" and similar expressions used herein are for illustrative purposes only.

[0090] In addition, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features. In the description of this application, the meaning of "multiple" is two or more, unless otherwise clearly and specifically defined. In this application, " / " means "or".

[0091] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0092] At present, during the charging and discharging process of lead-acid batteries, the high battery temperature and the corrosive acids or organic salts contained in the electrolyte will cause obvious corrosion of the positive electrode grid, making it impossible to obtain the grid composition in the initial state.

[0093] On this basis, the present invention provides a detection method and auxiliary equipment for analyzing the components of corroded grids in batteries, which are used to analyze the components of corroded grids in lead-acid batteries. The detection method of the present invention can avoid interference from corrosion layers and impurity elements in batteries, and the detection results are accurate.

[0094] The present invention is described in detail below in conjunction with a specific embodiment. In this embodiment, the lead-acid battery plates produced by the same process, the same production line, and the same batch are tested.

[0095] Examples 1-5

[0096] This embodiment analyzes the detection method of the corroded grid components in the battery, including the following steps:

[0097] 1. Prepare the sample. Specifically, the sample preparation includes the following steps:

[0098] (1) After dissecting the battery, remove the plates. Figure 1 As shown, remove the active material on the surface of the plate and take the inner grid of the battery, such as Figure 2 As shown, at this time the grid surface contains some adhered lead powder and corrosion layer.

[0099] (2) Place the grid in a container, treat it with a cleaning solution, then rinse it with pure water and dry it. The cleaning solution has a reducing property and can dissolve the residue on the surface of the grid, revealing the metallic color of the grid. Figure 3 shown.

[0100] In this embodiment, the cleaning liquid is a sugar-alkali solution, the mass percentage of sugar alkali in the sugar-alkali solution is 20%, the mass ratio of sugar to alkali in the sugar-alkali solution is 2:1, the sugar in the sugar-alkali solution is glucose, and the alkali is sodium hydroxide.

[0101] In this embodiment, the grid is subjected to a slight boiling treatment in a sugar-alkali solution under heating conditions, and the heating temperature is 85°C;

[0102] The sugar-alkali solution is selected in this embodiment because under alkaline conditions, glucose undergoes a ring-opening reaction to generate open-chain aldehydes and carboxylic acids, which have stronger reducing properties and can dissolve the surface material of the grid under heating conditions to reveal its metallic color, which is similar to the composition of the grid itself. At the same time, glucose and sodium hydroxide are easily available and low in cost.

[0103] (3) Take the dried grid or part of its structure and embed it in pure lead as a sample.

[0104] In this embodiment, part of the structure of the grid is the pole ear of the grid, that is, in this embodiment, the pole ear is embedded in pure lead as a sample. When handling the sample, care must be taken to make the sample flat and free of gaps to avoid interference with the detection data.

[0105] 2. Test the sample with a direct reading spectrometer and record the data

[0106] Since the positive grid is generally made of lead-calcium-tin-aluminum alloy, the lead-based general analysis procedure Pb-01 should be selected for testing the grid alloy, and the standard sample should be selected to calibrate the equipment first. If the Sn content of the alloy to be tested is about 1.2%, a lead alloy standard with a Sn content of about 1.2% can be selected for calibration. The same is true for other elements. Sometimes a standard sample can calibrate multiple elements at the same time. In order to ensure the accuracy of the results, argon with a purity greater than 99.999% should be selected as the protective gas. After calibrating the equipment, the sample is excited, and the same sample is excited at least twice, and the data is recorded.

[0107] In this embodiment, the direct reading spectrometer has the ability to detect elements such as Ca, Sn, Al, Ag, Cu, Bi, S, Te, Mg, and Pb.

[0108] The analysis spectra and detection limits of each element are as follows:

[0109] Ca: 315.887nm, 0.00020%-1.3%

[0110] Sn: 317.505nm, 0.00010%-1.3%

[0111] Al: 309.271nm, 0.000010%-0.0750%

[0112] Ag: 338.289nm, 0.000050%-0.0250%

[0113] Cu: 324.753nm, 0.00001%-0.0150%

[0114] Bi: 306.772nm, 0.000050%-1.2%

[0115] S: 180.731nm, 0.00010%-0.0110%

[0116] Te: 214.28nm, 0.00010%-0.100%

[0117] Mg: 279.077nm, 0.000050%-0.180%.

[0118] In the lead-based direct reading spectrometer, the Pb content is 100% minus the sum of other impurity elements. Ca, Sn, Al, Ag, Cu, Bi, S, Te, and Mg basically include the impurity elements present in lead.

[0119] The weight changes of the grids in Examples 1-5 are shown in Table 1.

[0120] Table 1 Weight change of grid treatment in Examples 1-5

[0121]

[0122] In the above-mentioned embodiment, due to the low content of glucose in the sugar-alkali solution, the oxide layer on the surface of the grid is not completely reduced.

[0123] In this embodiment, if the active substance needs to be analyzed, the following steps may also be included: wash the surface of the plate with water to pH 6-7, dry the plate, take out the plate after complete drying, and knock off the active substance for testing. The active substance here mainly refers to the substance involved in the electrochemical reaction in the battery. The positive electrode active substance is closely related to the charge and discharge state of the battery. When dissecting the battery, the discharge state can be judged according to the lead dioxide content in the active substance. At present, the active substance is generally titrated with EDTA solution.

[0124] Embodiment 6-10

[0125] When the grid is cleaned with a sugar-alkali solution, due to the large surface area of ​​the grid and the large corrosion area, the sugar-alkali solution is consumed too quickly, which is easy to cause waste. In addition, the subsequent operation only processes the tabs. Therefore, in order to avoid waste and save costs, the applicant usually cuts off the grid tabs first, and then puts the tabs into the sugar-alkali solution for a slight boiling treatment. Specifically, the detection method for analyzing the components of the corroded grid in the battery in this embodiment includes the following steps:

[0126] 1. Prepare the sample. Specifically, the sample preparation includes the following steps:

[0127] (1) After dissecting the battery, take out the plates, remove the active materials on the surface of the plates, and take out the grid inside the battery. At this time, the surface of the grid contains some adhered lead powder and corrosion layer.

[0128] (2) Take part of the grid structure and place it in a container, treat it with a cleaning solution, then wash it with pure water and dry it. The cleaning solution has a reducing property and can dissolve the residue on the surface of the grid, revealing the metallic color of the grid.

[0129] In this embodiment, the cleaning liquid is a sugar-alkali solution, the mass percentage of sugar alkali in the sugar-alkali solution is 20%, the mass ratio of sugar to alkali in the sugar-alkali solution is 3:1, the sugar in the sugar-alkali solution is glucose, and the alkali is sodium hydroxide.

[0130] In this embodiment, the grid is subjected to a slight boiling treatment in a sugar-alkali solution under heating conditions, and the heating temperature is 90°C;

[0131] In this embodiment, part of the structure of the grid is the pole ear of the grid, that is, in this embodiment, the pole ear is placed in a container, treated with a cleaning solution, then cleaned with pure water, and dried.

[0132] (3) Take the dried tab and embed it in pure lead as a sample. When handling the sample, pay attention to the flatness of the sample and no gaps to avoid interference with the test data.

[0133] 2. Test the sample with a direct reading spectrometer and record the data

[0134] Since the positive grid is generally made of lead-calcium-tin-aluminum alloy, the lead-based general analysis procedure Pb-01 should be selected for testing the grid alloy, and the standard sample should be selected to calibrate the equipment first. If the Sn content of the alloy to be tested is about 1.2%, a lead alloy standard with a Sn content of about 1.2% can be selected for calibration. The same is true for other elements. Sometimes a standard sample can calibrate multiple elements at the same time. In order to ensure the accuracy of the results, argon with a purity greater than 99.999% should be selected as the protective gas. After calibrating the equipment, excite the sample, and excite the same sample at least twice, and record the data.

[0135] In this embodiment, the direct reading spectrometer has the ability to detect elements such as Ca, Sn, Al, Ag, Cu, Bi, S, Te, Mg, and Pb.

[0136] The analysis spectra and detection limits of each element are as follows:

[0137] Ca: 315.887nm, 0.00020%-1.3%

[0138] Sn: 317.505nm, 0.00010%-1.3%

[0139] Al: 309.271nm, 0.000010%-0.0750%

[0140] Ag: 338.289nm, 0.000050%-0.0250%

[0141] Cu: 324.753nm, 0.00001%-0.0150%

[0142] Bi: 306.772nm, 0.000050%-1.2%

[0143] S: 180.731nm, 0.00010%-0.0110%

[0144] Te: 214.28nm, 0.00010%-0.100%

[0145] Mg: 279.077nm, 0.000050%-0.180%.

[0146] In the lead-based direct reading spectrometer, the Pb content is 100% minus the sum of other impurity elements. Ca, Sn, Al, Ag, Cu, Bi, S, Te, and Mg basically include the impurity elements present in lead.

[0147] The weight changes of the grids in Examples 6-10 are shown in Table 2.

[0148] Table 2 Weight changes of grids in Examples 6-10

[0149]

[0150]

[0151] In this embodiment, if the active substance needs to be analyzed, the following steps may also be included: wash the surface of the plate with water to pH 6-7, dry the plate, take out the plate after complete drying, and knock off the active substance for testing. The active substance here mainly refers to the substance involved in the electrochemical reaction in the battery. The positive electrode active substance is closely related to the charge and discharge state of the battery. When dissecting the battery, the discharge state can be judged according to the lead dioxide content in the active substance. At present, the active substance is generally titrated with EDTA solution.

[0152] Examples 11-15

[0153] The detection method in Examples 11-15 is different from the detection method in Examples 6-10 in that the cleaning solution is a sugar-alkali solution, the mass percentage of sugar alkali in the sugar-alkali solution is 20%, the mass ratio of sugar to alkali in the sugar-alkali solution is 4:1, the sugar in the sugar-alkali solution is glucose, and the alkali is sodium hydroxide.

[0154] In this embodiment, the grid is subjected to a slight boiling treatment in a sugar-alkali solution under heating conditions, and the heating temperature is 95° C.; the other details are the same.

[0155] The weight changes of the grids in Examples 11-15 are shown in Table 3.

[0156] Table 3 Weight changes of grids in Examples 11-15

[0157]

[0158] Examples 16-20

[0159] The detection method in Examples 16-20 is different from the detection method in Examples 6-10 in that the cleaning solution is a sugar-alkali solution, the mass percentage of sugar alkali in the sugar-alkali solution is 20%, the mass ratio of sugar to alkali in the sugar-alkali solution is 5:1, the sugar in the sugar-alkali solution is glucose, and the alkali is sodium hydroxide.

[0160] In this embodiment, the grid is subjected to a slight boiling treatment in a sugar-alkali solution under heating conditions, and the heating temperature is 100° C.; the other details are the same.

[0161] The weight changes of the grid treatments in Examples 16-20 are shown in Table 4.

[0162] Table 4 Weight change of grid treatment in Examples 16-20

[0163]

[0164] Examples 21-25

[0165] The detection method in Examples 21-25 is different from the detection method in Examples 6-10 in that the cleaning solution is a sugar-alkali solution, the mass percentage of sugar alkali in the sugar-alkali solution is 20%, the mass ratio of sugar to alkali in the sugar-alkali solution is 3:1, the sugar in the sugar-alkali solution is glucose, and the alkali is sodium hydroxide.

[0166] In this embodiment, the grid is subjected to a slight boiling treatment in a sugar-alkali solution under heating conditions, the heating temperature is 70±5° C., and the other details are the same.

[0167] The weight changes of the grid treatments in Examples 21-25 are shown in Table 5.

[0168] Table 5 Weight change of grid treatment in Examples 21-25

[0169]

[0170]

[0171] Comparative Examples 1-5

[0172] The difference between the detection method in Comparative Examples 1-5 and the detection method in Examples 6-10 is that the cleaning liquid is a sodium bicarbonate solution, and the mass percentage of sodium bicarbonate is 20%.

[0173] In this comparative example, the grid is subjected to a slight boiling treatment in a sodium bicarbonate solution under heating conditions, the heating temperature is 90° C., and the other details are the same.

[0174] The weight changes of the grid treatments in Comparative Examples 1-5 are shown in Table 6.

[0175] Table 6 Weight change of grid treatment in comparative examples 1-5

[0176]

[0177] The comparative example reacts slowly because the sodium bicarbonate is thermally decomposed and loses effectiveness during the heating process.

[0178] Comparative Examples 6-10

[0179] The difference between the detection method in Comparative Example 6-10 and the detection method in Example 6-10 is that the electrolyte environment is simulated. In the lead-acid battery, the electrolyte is sulfuric acid. Here, the concentration is 1.255 g / cm 3 of sulfuric acid for cleaning.

[0180] In this comparative example, the grid was subjected to a micro-boiling treatment under heating conditions, the heating temperature was 90° C., and the other details were the same.

[0181] The weight changes of the grid treatments in Comparative Examples 6-10 are shown in Table 7.

[0182] Table 7 Weight change of grid treatment in comparative examples 6-10

[0183]

[0184] In this comparative example, lead sulfate generated during the discharge process adheres to the surface of the plate and does not react with sulfuric acid.

[0185] The direct reading spectrometer data of Examples 1, 6, 11, 16, 21 and Comparative Examples 1 and 6 are shown in Table 8.

[0186] Table 8 Direct reading spectrometer data table of Examples 1, 6, 11, 16, 21 and Comparative Examples 1 and 6

[0187]

[0188] It can be seen from Table 8 that the detection method of the present invention can avoid the interference of impurity elements in the corrosion layer and the battery, and the detection result is accurate.

[0189] Since the tabs are small, they are not easy to take out from the container, and the glucose undergoes caramelization reaction, and the solution gradually changes from transparent to brown and black, making it impossible to determine whether the tabs are cleaned through the beaker. To solve the above technical problems, the present invention provides the following specific embodiments.

[0190] like Figure 4-6 As shown, an auxiliary device for the detection method as described above is used to analyze the components of the corroded grid in the battery, including a box body 1, a lifting basket 2, and a driving mechanism.

[0191] In this embodiment, the box body 1 is made of high temperature and alkali resistant ceramic material and is used to place cleaning liquid. The box body 1 includes a bottom and side walls extending upward from the bottom, and the bottom and the side walls together enclose a space for accommodating the cleaning liquid.

[0192] In this embodiment, the lifting basket 2 is arranged in the box body 1 and can move up and down relative to the box body 1, the grid or its partial structure is placed in the lifting basket 2, and the driving mechanism is used to drive the lifting basket 2 to move up and down. In this embodiment, the partial structure of the grid is the pole ear of the grid.

[0193] Specifically, four support columns 11 are arranged on the inner side of the side wall of the box body 1, and the lifting basket 2 is slidably arranged on the support columns 11. The driving mechanism drives the lifting basket 2 to slide up and down, which is used to adjust the height of the lifting basket 2, so as to facilitate observation of the current cleaning status of the grid or the tab. The driving mechanism here can be electric or manual, the electric one can be driven by a motor, and the manual one can be driven by a hand-cranked rocker.

[0194] In this embodiment, the side wall of the lifting basket 2 is set as a transparent plate, which can be made of a light-transmitting material, preferably polyhexamethylene terephthalamide. This material has a high light transmittance, which makes it easy to observe the state of the pole ears in the lifting basket 2, and has the characteristics of high temperature resistance and stable chemical properties, which meets the requirements.

[0195] In this embodiment, the bottom of the lifting basket 2 is provided with a plurality of through holes 21. At the same time, the area of ​​the plurality of through holes 21 is greater than or equal to 1 / 3 of the bottom area of ​​the lifting basket 2 and less than or equal to 2 / 3 of the bottom area of ​​the lifting basket 2.

[0196] The provision of the through hole 21 ensures that the state of the grid can be observed more clearly when the lifting basket 2 is raised. At the same time, the limitation on the area of ​​the through hole 21 ensures the strength of the lifting basket 2 on the one hand, and the descending speed of the sugar-alkali solution on the other hand, which is convenient for observation and saves time.

[0197] In this embodiment, a partition plate 24 is provided in the lifting basket 2, and the partition plate 24 divides the interior of the lifting basket 2 into at least two storage spaces 22. Specifically, in this embodiment, there are six storage spaces 22. The partition plate 24 is provided with a plurality of connection holes 23, and adjacent storage spaces 22 are connected through the connection holes 23. The area of ​​the plurality of connection holes 23 provided on the partition plate 24 accounts for 1 / 3-2 / 3 of the area of ​​the partition plate 24.

[0198] The setting of multiple storage spaces 22 can clean multiple plate grid ears at the same time to improve efficiency. The limitation of the connection hole 23, on the one hand, ensures the strength of the lifting basket 2, and on the other hand, when the lifting basket 2 is raised, it is conducive to the descending of the sugar-alkali solution to expose the pole ears, which is convenient for observing the cleaning degree of the pole ears.

[0199] In this embodiment, a heating device 3 is provided at the bottom of the box 1 to heat the cleaning liquid. The heating device 3 is a conventional method.

[0200] In this embodiment, a stirring device 4 is provided at the bottom center of the box 1 to stir the cleaning liquid to ensure a uniform temperature of the liquid in the box 1 and prevent the sugar-alkali solution from suddenly boiling over and overflowing to injure people.

[0201] In this embodiment, a drainage device 5 is provided at the bottom of the box 1, and the drainage device 5 includes a water outlet located at the bottom of the box 1. The drainage device 5 is used to drain the sugar-alkali solution inside the box 1 and the waste liquid for cleaning the instrument through the water outlet and collect and reprocess it to prevent the test liquid and residual liquid from polluting the environment.

[0202] In this embodiment, a control panel is also provided on the box body 1, and the lifting height of the lifting basket 2, the heating of the heating device 3, and the stirring of the stirring device 4 can all be operated through the control panel. The operating circuit of the control panel is conventional.

[0203] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0204] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A method for analyzing the components of corroded grids in a battery, characterized in that: The steps include: Prepare the test specimen; Test the sample with a direct reading spectrometer and record the data; The preparation of the sample includes: Take a battery inner grid; The grid is treated with a cleaning solution, then cleaned with pure water and dried, wherein the cleaning solution has reducing properties and can dissolve the residue on the surface of the grid, so that the grid reveals its metallic color; The grid or part of its structure after drying is embedded in pure lead as a sample.

2. The method for detecting the corroded grid components in the analytical battery according to claim 1, characterized in that: The cleaning solution is a sugar-alkali solution, and the mass percentage of sugar-alkali in the sugar-alkali solution is 10%-40%; Preferably, the mass ratio of sugar to alkali in the sugar-alkali solution is 3.0:1-4.3:1; Preferably, the sugar in the sugar-alkali solution is glucose, and the alkali is sodium hydroxide; Preferably, the cleaning liquid treatment is carried out under heating conditions, and the heating temperature is 85-105°C; Preferably, a partial structure of the grid is a lug of the grid.

3. The method for detecting corroded grid components in an analytical cell according to claim 1, characterized in that: The specific operation of testing the sample with the direct reading spectrometer is to select the lead-based general analysis program Pb-01, select the standard sample to calibrate the equipment, then excite the sample, excite the same sample at least twice, and record the data; Preferably, the direct reading spectrometer has the ability to detect elements such as Ca, Sn, Al, Ag, Cu, Bi, S, Te, Mg, and Pb. The analysis spectra and detection limits of each element are as follows: Ca: 315.887nm, 0.00020%-1.3% Sn: 317.505nm, 0.00010%-1.3% Al: 309.271nm, 0.000010%-0.0750% Ag: 338.289nm, 0.000050%-0.0250% Cu: 324.753nm, 0.00001%-0.0150% Bi: 306.772nm, 0.000050%-1.2% S: 180.731nm, 0.00010%-0.0110% Te: 214.28nm, 0.00010%-0.100% Mg: 279.077nm, 0.000050%-0.180%.

4. A method for analyzing the components of corroded grids in a battery, characterized in that: The steps include: Prepare the test specimen; Test the sample with a direct reading spectrometer and record the data; The preparation of the sample includes: Take a battery inner grid; Treating a portion of the grid structure with a cleaning solution, then washing it with pure water, and air-drying it, wherein the cleaning solution has a reducing property and can dissolve the residue on the surface of the portion of the grid structure, so that the portion of the grid structure reveals its metallic color; A part of the grid structure after drying is embedded in pure lead as a sample.

5. The method for detecting corroded grid components in an analytical cell according to claim 4, characterized in that: The cleaning solution is a sugar-alkali solution, and the mass percentage of sugar-alkali in the sugar-alkali solution is 10%-40%; Preferably, the mass ratio of sugar to alkali in the sugar-alkali solution is 3.0:1-4.3:1; Preferably, the sugar in the sugar-alkali solution is glucose, and the alkali is sodium hydroxide; Preferably, the cleaning liquid treatment is carried out under heating conditions, and the heating temperature is 85-105°C; Preferably, a partial structure of the grid is a lug of the grid.

6. The detection method for analyzing the components of corroded grids in a battery according to claim 4, characterized in that: The specific operation of the parameter setting of the direct reading spectrometer for testing the sample is to select the lead-based general analysis program Pb-01, select the standard sample to calibrate the equipment, and then excite the sample, excite the same sample at least twice, and record the data; Preferably, the direct reading spectrometer has the ability to detect elements such as Ca, Sn, Al, Ag, Cu, Bi, S, Te, Mg, and Pb. The analysis spectra and detection limits of each element are as follows: Ca: 315.887nm, 0.00020%-1.3% Sn: 317.505nm, 0.00010%-1.3% Al: 309.271nm, 0.000010%-0.0750% Ag: 338.289nm, 0.000050%-0.0250% Cu: 324.753nm, 0.00001%-0.0150% Bi: 306.772nm, 0.000050%-1.2% S: 180.731nm, 0.00010%-0.0110% Te: 214.28nm, 0.00010%-0.100% Mg: 279.077nm, 0.000050%-0.180%.

7. An auxiliary device for the detection method according to any one of claims 1 to 6, characterized in that: It includes a box body, a lifting basket, and a driving mechanism. The box body is used to place cleaning liquid. The lifting basket is arranged in the box body and can move up and down relative to the box body. The grid or part of its structure is placed in the lifting basket. The driving mechanism is used to drive the lifting basket to move.

8. The auxiliary device for the detection method according to claim 7, characterized in that: A heating device is provided in the box body to heat the cleaning liquid; Preferably, a stirring device is provided in the box to stir the cleaning liquid; Preferably, the stirring device is arranged at the bottom center of the box body; Preferably, a partial structure of the grid is a lug of the grid.

9. The auxiliary device for the detection method according to claim 7, characterized in that: The bottom of the lifting basket is provided with a through hole, and the number of the through holes is multiple; Preferably, the area of ​​the plurality of through holes is greater than or equal to 1 / 3 of the bottom area of ​​the lifting basket, and less than or equal to 2 / 3 of the bottom area of ​​the lifting basket; Preferably, a partition plate is provided in the lifting basket, and the partition plate divides the interior of the lifting basket into at least two storage spaces; Preferably, the partition plate is provided with a connection hole, the number of the connection holes is multiple, and the adjacent storage spaces are connected through the connection holes; Preferably, the side wall of the lifting basket is configured as a transparent plate; Preferably, the area of ​​the plurality of connection holes provided on the partition plate occupies 1 / 3-2 / 3 of the area of ​​the partition plate.

10. The auxiliary device for the detection method according to claim 7, characterized in that: A drainage device is arranged at the bottom of the box body.

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