A method for battery leak detection based on a riboflavin derivative and applications thereof

Abstract

The application belongs to the technical field of battery safety detection, and particularly relates to a battery leakage detection method based on a riboflavin derivative and application. The method is based on the stable fluorescence characteristics of riboflavin. When a battery is prepared, the riboflavin is modified and purified, and the riboflavin derivative is selectively added to the electrolyte, so that the riboflavin derivative remains stable in nature when added to the electrolyte of an acid or alkali or organic solvent, and has good solubility with the electrolyte. When detection is performed, only the surface of the battery needs to be irradiated by using an ultraviolet lamp, and the purpose of quickly and batch detecting electrolyte leakage of the battery can be achieved by naked eye observation.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of battery safety detection, and particularly relates to a battery leakage detection method based on a riboflavin derivative and application. BACKGROUND

[0002] During use, a battery may swell and deform or its shell may crack due to reasons such as aging, high temperature, impact, and internal abnormal chemical reaction, resulting in electrolyte leakage. Battery electrolytes can be divided into three categories: acidic electrolyte, alkaline electrolyte, and organic electrolyte.

[0003] The main component of the acidic electrolyte is sulfuric acid solution, such as lead-acid batteries, acidic zinc-manganese batteries, etc.

[0004] The main component of the alkaline electrolyte is potassium hydroxide solution, such as cadmium-nickel batteries, nickel-hydrogen batteries, and alkaline zinc-manganese batteries. Organic electrolyte is represented by lithium ion battery electrolyte, which is generally composed of lithium salt and one or more non-aqueous organic solvents, and usually one or several additives are added to the electrolyte to make it have more excellent performance. Lithium salt is mainly divided into inorganic lithium salt and organic lithium salt, inorganic lithium salt includes lithium hexafluorophosphate (LiPF6), lithium perchlorate (LiClO4), lithium hexafluoroarsenate (LiAsF6), lithium tetrafluoroborate (LiBF4), etc. Organic lithium salt includes lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiODFB), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), and lithium bis(fluorosulfonyl)imide (LiFSI). The solvent is mainly carbonic acid ester, which is divided into cyclic carbonic acid ethylene ester (EC), carbonic acid propylene ester (PC), chain carbonic acid dimethyl ester (DMC), carbonic acid diethyl ester (DEC), and carbonic acid methyl ethyl ester (EMC). Electrolyte additives, such as film-forming agents, include vinylene carbonate (VC), vinylene ethylene carbonate (VEC), fluoroethylene carbonate (FEC), and Li2CO3.

[0005] As can be seen from the above electrolyte components, most of the electrolytes are flammable or combustible, and when they leak, they will burn violently when encountering an ignition source, further reacting with other structural materials of the battery to cause battery thermal runaway, which has serious fire and explosion hazards.

[0006] In addition, the electrolyte components have certain acute oral toxicity, acute dermal toxicity, acute inhalation toxicity, skin corrosion / stimulation, severe eye damage / eye irritation, specific target organ toxicity, and other health hazards, which should be strictly prevented from contacting the human body. At the same time, the above components also have certain ecological toxicity, which is enough to harm the aquatic environment and soil, and are prohibited from being randomly discarded and discharged into sewers or water bodies. Therefore, it is very important to detect the electrolyte leakage of the battery and timely find the electrolyte leakage.

[0007] Currently, the detection methods for battery electrolyte leakage mainly include manual observation method and pressure detection method. The manual observation method relies on the experience of the detection personnel, and it is difficult to accurately identify the early stage of electrolyte leakage. The pressure detection method detects the interaction between the electrolyte leakage and the environmental pressure. Specifically, it can be divided into two types. One is to vacuum the battery, form a large pressure difference outside the leaking battery, and the electrolyte leaks in large quantities at the micro leakage point due to the gas pressure, and then the appearance is detected. The other is that the electrolyte leakage volatilizes, causing the environmental pressure to rise, and the pressure sensor is used for testing. The above two methods are only suitable for the detection of single battery, and the detection steps are complicated, which is not suitable for the daily detection of batch batteries.

[0008] Riboflavin has a large conjugated structure, good fluorescence effect and is cheap and easy to obtain, and is a good fluorescent detection reagent. However, riboflavin molecules are unstable in acidic or alkaline environments, and have poor solubility in some solvents, so they have not been applied in the field of battery safety. SUMMARY

[0009] In view of the problems in the background art, the technical problem to be solved by the present application is to provide a battery leakage detection method based on riboflavin derivatives and applications to solve at least one problem in the background art. The method is based on the stable fluorescence properties of riboflavin. By adding riboflavin derivatives to the electrolyte during the preparation of the battery according to the different properties of the electrolyte, the properties of the electrolyte remain stable after adding to the acidic or alkaline electrolyte, and the performance of the battery is not affected. At the same time, it has good solubility in organic electrolyte. When detecting, only the surface of the battery is irradiated by using an ultraviolet lamp, and the purpose of quickly and batch detecting the electrolyte leakage of the battery can be achieved by observing with the naked eye.

[0010] The technical scheme adopted is:

[0011] A battery leakage detection method based on riboflavin derivatives, during the preparation of the electrolyte, the riboflavin is modified and purified, and the riboflavin derivatives are selectively added to the electrolyte, so that the properties of the electrolyte remain stable after being added to the acidic or alkaline or organic solvent electrolyte, and at the same time, the electrolyte has good solubility; during detection, the surface of the battery is irradiated by using an ultraviolet lamp, and the purpose of quickly and batch detecting the electrolyte leakage of the battery can be achieved by observing with the naked eye.

[0012] Preferably, the modification method of riboflavin includes halogenation, alkylation or esterification to ensure that the target molecule is stable under acidic, alkaline and organic solvent conditions and has fluorescence activity.

[0013] Preferably, for the acid battery whose electrolyte composition is mainly sulfuric acid solution, the hydroxyl group in the riboflavin molecule is halogenated for protection, and the specific steps are as follows:

[0014] (1) Dissolve riboflavin in anhydrous ether solvent, then add triethylamine;

[0015] (2) Slowly add phosphorus trichloride or phosphorus tribromide in proper amount under ice bath condition, after the addition is completed, react for 6-12 hours under ice water bath condition, the reaction equation (halogenation reaction) is as follows:

[0016]

[0017] The whole reaction process must be carried out under the protection of inert gas such as nitrogen or argon, and the reaction progress is monitored by thin layer chromatography (using prior art) during the reaction process;

[0018] (3) After the reaction is completed, filter out the generated triethylamine phosphite in the system, add silica gel (in proper amount) into the solution, remove the ether solvent in the system by rotary evaporation, and obtain a dry powder mixture of the reaction product and silica gel;

[0019] (4) Lay the mixed powder on the upper part of a silica gel column, and separate by column chromatography with eluent to obtain the product part with the smallest polarity and eluted first from the chromatographic column.

[0020] After the eluent is evaporated by rotary evaporation, a light yellow or dark yellow halogenated riboflavin derivative is obtained.

[0021] As a further preferred, the anhydrous ether solvent includes diethyl ether, propyl ether, isopropyl ether, methyl tert-butyl ether, anisole, tetrahydrofuran, dioxane, and the concentration ranges from 0.01 to 2 mol / L; but the anhydrous ether solvent used in the present application includes but is not limited to the above-mentioned types.

[0022] The ratio of triethylamine to riboflavin is greater than 4:1.

[0023] As a further preferred, the ratio of phosphorus trichloride or phosphorus tribromide to riboflavin is greater than 1.4:1.

[0024] As a further preferred, the eluent is a mixture of petroleum ether and toluene, and the volume ratio of toluene to petroleum ether is 1:5-20.

[0025] For the alkaline battery with potassium hydroxide solution as the main component of the electrolyte, the imide in the riboflavin molecule is alkylated and protected, and the specific steps are as follows:

[0026] (1) Dissolve riboflavin in a protic solvent, and add 1-1.1 equivalent of strong base in the solution system, and stir at room temperature;

[0027] (2) After the base is completely dissolved, slowly add 1-1.1 equivalent of monohalogenated alkane to the solution, and stir at normal temperature and pressure for 6-12 hours after the addition of halogenated alkane is completed, and the reaction equation (alkylation reaction) is as follows:

[0028]

[0029] The reaction progress is monitored by thin layer chromatography during the reaction;

[0030] (3) After the reaction is completed, a weak acid is added to neutralize the excess base, and then the inorganic salt generated in the reaction is filtered out;

[0031] (4) Silica gel (an appropriate amount) is added to the reaction solution, and the protic solvent in the system is removed by rotary evaporation to obtain a dry powder mixture of the reaction product and silica gel;

[0032] (5) The mixed powder is laid on the upper part of the silica gel column, and eluent is used for column chromatography separation to obtain the product part with the smallest polarity and eluted first from the chromatographic column;

[0033] (6) The eluent is evaporated by rotary evaporation to obtain a white or light yellow alkyl-protected riboflavin derivative.

[0034] As a further preferred, the protic solvent includes methanol, ethanol, propanol, butanol, isobutanol, tert-butanol, with a concentration range of 0.05-2 mol / L;

[0035] However, the protic solvent used in the present application includes but is not limited to the above-mentioned types.

[0036] As a further preferred, the strong base includes lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide;

[0037] However, the strong base used in the present application includes but is not limited to the above-mentioned types.

[0038] As a further preferred, the monohalogenated alkane includes bromoethane, bromopropane, n-butyl chloride, chlorinated tert-butane, brominated tert-butane, chlorinated cyclopentane, brominated cyclopentane;

[0039] However, the monohalogenated alkane used in the present application includes but is not limited to the above-mentioned types.

[0040] As a further preferred, the eluent is a mixture of petroleum ether and ethyl acetate, and the volume ratio of ethyl acetate to petroleum ether is 1:10-50.

[0041] Preferably, for the lithium ion battery with ethylene carbonate, propylene carbonate, chain dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate as the electrolyte solvent components, the esterification reaction is carried out on the hydroxyl group on the side chain of the riboflavin molecule, and the specific steps are as follows:

[0042] (1) Dissolve riboflavin in an organic solvent, and then add triethylamine;

[0043] (2) slowly add acetyl chloride in proper amount under ice bath condition, after the addition is completed, react for 6-12h under ice water bath condition, the reaction equation (esterification reaction) is as follows:

[0044]

[0045] The whole reaction process is carried out under anhydrous dry condition (that is, the container containing the reactants must be anhydrous dry), and the reaction progress is monitored by thin layer chromatography during the reaction process;

[0046] (3) after the reaction is completed, the generated triethylamine hydrochloride in the system is filtered out;

[0047] (4) add silica gel in the solution, remove the ether solvent in the system by rotary evaporation, and obtain a dry powder mixture of the reaction product and silica gel;

[0048] (5) the mixed powder is laid on the upper part of the silica gel column, and column chromatography separation is carried out with eluent of petroleum ether: ethyl acetate = 100:1 to 5:1, to obtain the product part with the minimum polarity and eluted first from the chromatographic column;

[0049] (6) after the eluent is evaporated by rotary evaporation, a light yellow esterified riboflavin derivative is obtained.

[0050] As a further preferred, the organic solvent is a non-alcohol solvent stable under acidic conditions, including dichloromethane, ethyl acetate, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, with a concentration range of 0.01-2mol / L; the organic solvent used in the application includes but is not limited to the above types.

[0051] The ratio of triethylamine to riboflavin is greater than 4:1, the ratio of acetyl chloride to riboflavin is greater than 4:1, and the amount of acetyl chloride is less than the amount of triethylamine.

[0052] As a further preferred, the eluent is a mixture of petroleum ether and ethyl acetate, wherein the volume ratio of ethyl acetate to petroleum ether is 1:5-100.

[0053] A battery leakage detection method based on riboflavin derivatives is applied to the leakage detection of batteries using electrolyte, including lithium batteries, lead-acid batteries, cadmium-nickel batteries, nickel-hydrogen batteries, zinc-silver batteries, alkaline zinc-manganese batteries, and acid zinc-manganese batteries, and can also be used for monitoring of battery packs.

[0054] Compared with the prior art, the present application has the advantages of:

[0055] The present invention incorporates a synthetically modified riboflavin derivative that is compatible with the electrolyte and has stable fluorescence properties during the battery production process. This allows for direct determination of electrolyte leakage through ultraviolet light scanning and visual observation, thus solving the problem of difficulty in determining battery leakage.

[0056] This method is applicable to both the detection of individual cells and the monitoring of battery packs. Attached Figure Description

[0057] Figure 1 This is a schematic diagram of the detection method of the present invention. Detailed Implementation

[0058] The accompanying drawings are for illustrative purposes only; some parts may be omitted, enlarged, or reduced to better illustrate this embodiment, and do not represent the actual product dimensions.

[0059] For those skilled in the art, certain well-known structures and their descriptions in the accompanying drawings may be omitted, and therefore should not be construed as limiting the present invention.

[0060] To make the technical means, creative features, achieved objectives, and effects of this invention readily understandable, the invention will be further described in detail below with reference to embodiments and accompanying drawings. Obviously, the accompanying drawings described below are from some embodiments of this invention. For those skilled in the art, other drawings can be obtained from these drawings without any creative effort.

[0061] Example 1

[0062] like Figure 1 As shown, a battery leakage detection method based on riboflavin derivatives involves modifying and purifying riboflavin during the preparation of the electrolyte battery, and selectively adding riboflavin derivatives to the electrolyte to ensure that the derivatives remain stable in acidic or alkaline electrolytes, exhibit fluorescence activity, and have good solubility in the electrolyte.

[0063] During testing, ultraviolet lamps are used to irradiate the surface of the battery, and battery electrolyte leakage can be quickly detected in batches by visual inspection.

[0064] In this embodiment, the lead-acid battery whose electrolyte is mainly sulfuric acid solution needs to have the hydroxyl groups in the riboflavin molecule halogenated to prevent them from etherifying in the electrolyte and causing changes in properties.

[0065] The specific steps are as follows:

[0066] Prepare a 500 mL, 1 mol / L riboflavin ether solution.

[0067] In the solution, 2.05 mol triethylamine was added, and 0.7 mol phosphorus trichloride was slowly added dropwise under ice bath conditions. After the dropwise addition was completed, the reaction was carried out under ice water bath conditions for 6 h, and the entire reaction process was protected by argon without water and oxygen. The reaction progress was monitored by thin layer chromatography during the reaction process.

[0068] After the reaction was completed, the triethylamine phosphite generated in the system was filtered out, and an appropriate amount of silica gel was added to the solution. The ethyl ether solvent in the system was removed by rotary evaporation to obtain a dry powder mixture of the reaction product and silica gel.

[0069] The mixed powder was laid on the upper part of the silica gel column, and column chromatography separation was carried out using an eluent of petroleum ether:toluene = 10:1 to obtain the product with the smallest polarity and the first eluted product from the chromatographic column.

[0070] The eluent was rotary evaporated to obtain a light yellow chlorinated lutein derivative, and the reaction yield was 73%.

[0071] The lutein molecule modified by the above method was added to the electrolyte of a lead-acid battery, and the concentration was controlled to be 1 mmol / L. A small amount of solution was dropped on a thin layer chromatography plate, and fluorescence could be observed with the naked eye under ultraviolet light. In a 5 mol / L H2SO4 solution environment, no ether compound was detected within 72 h.

[0072] Example 2

[0073] A battery leakage detection method based on lutein derivatives, in this embodiment, the main component of the electrolyte of the lead-acid battery is sulfuric acid solution. The hydroxyl group in the lutein molecule needs to be halogenated to prevent etherification in the electrolyte and cause changes in properties.

[0074] The specific steps are as follows:

[0075] A 500 mL, 1 mol / L lutein tetrahydrofuran solution was prepared.

[0076] In the solution, 2.05 mol triethylamine was added, and 0.7 mol phosphorus tribromide was slowly added dropwise under ice bath conditions. After the dropwise addition was completed, the reaction was carried out under ice water bath conditions for 10 h, and the entire reaction process was protected by argon without water and oxygen. The reaction progress was monitored by thin layer chromatography during the reaction process.

[0077] After the reaction was completed, the triethylamine phosphite generated in the system was filtered out, and an appropriate amount of silica gel was added to the solution. The tetrahydrofuran solvent in the system was removed by rotary evaporation to obtain a dry powder mixture of the reaction product and silica gel.

[0078] The mixed powder was laid on the upper part of the silica gel column, and column chromatography separation was carried out using an eluent of petroleum ether:toluene = 5:1 to obtain the first eluted product from the column.

[0079] The eluent was rotary evaporated to obtain orange-yellow chlorinated riboflavin derivative, and the reaction yield was 60%.

[0080] The riboflavin molecule modified by the above method was added to the electrolyte of a lead-acid battery, and the concentration was controlled to be 0.5 mmol / L. A small amount of solution was dropped on a thin layer chromatography plate, and fluorescence could be observed with the naked eye under ultraviolet light. And in the environment of 5 mol / L H2SO4 solution, no ether compound was detected within 72 h.

[0081] Example 3

[0082] A battery leakage detection method based on riboflavin derivative, in this embodiment, the main component of the electrolyte is a zinc-manganese battery of potassium hydroxide alkaline battery solution, and the imide in the riboflavin molecule needs to be alkylated to prevent its hydrolysis in alkaline environment and cause changes in properties.

[0083] The specific steps are as follows:

[0084] Prepare 500 mL of 1 mol / L riboflavin ethanol solution.

[0085] Add 0.55 mol of potassium tert-butoxide to the solution, and slowly add 0.5 mol of chloro-tert-butane under ice bath conditions. After the addition is completed, react at room temperature for 6 h in a water-free environment. During the reaction, the progress of the reaction was monitored by thin layer chromatography.

[0086] After the reaction is completed, a small amount of boric acid is added to remove the remaining base in the system, and the generated potassium chloride in the system is filtered out. An appropriate amount of silica gel is added to the solution, and the ethanol solvent in the system is removed by rotary evaporation to obtain a mixture of dry powder of reaction product and silica gel.

[0087] The mixed powder is laid on the upper part of the silica gel column, and petroleum ether: ethyl acetate = 30:1 range of eluent is used for column chromatography separation to obtain the first eluted part of the product from the column.

[0088] The eluent was rotary evaporated to obtain a light yellow tert-butyl substituted riboflavin derivative, and the reaction yield was 81%.

[0089] The riboflavin molecule modified by the above method was added to the electrolyte of a zinc-manganese alkaline battery, and the concentration was controlled to be 0.1 mmol / L. A small amount of solution was dropped on a thin layer chromatography plate, and fluorescence could be observed with the naked eye under ultraviolet light. And in the environment of 10 mol / L KOH solution, no hydrolysis product was detected within 72 h.

[0090] Example 4

[0091] A kind of battery leakage detection method based on riboflavin derivative, in the embodiment, the main component of electrolyte is lithium hexafluorophosphate battery solution of potassium hydroxide alkaline battery solution, acylimide in riboflavin molecule needs to be alkylated protection, prevent its hydrolysis in alkaline environment causes property change.

[0092] Specific steps are as follows:

[0093] 500 mL, 1 mol / L riboflavin methanol solution is configured.

[0094] 0.55 mol sodium ethoxide is added to the solution, 0.5 mol chlorocyclohexane is slowly added under ice bath condition, after dropwise addition is completed, reaction is carried out for 8 h under anhydrous room temperature environment, and reaction progress is monitored by thin layer chromatography during reaction.

[0095] After reaction is completed, a small amount of boric acid is added to remove residual base in the system, sodium chloride generated in the system is filtered out, appropriate silica gel is added to the solution, methanol solvent in the system is removed by rotary evaporation, and dry powder of the reaction product and silica gel mixture is obtained.

[0096] The mixed powder is laid on the upper part of silica gel column, and column chromatography separation is carried out using eluent in the range of petroleum ether: ethyl acetate=50:1, to obtain the first eluted part of the product from the column.

[0097] After the eluent is rotary evaporated, yellowish tert-butyl-substituted riboflavin derivative is obtained, and the reaction yield is 81%.

[0098] The riboflavin molecule modified by the above method is added to the lithium hexafluorophosphate battery electrolyte, the concentration is controlled to be 0.1 mmol / L, a small amount of solution is dropped on the thin layer chromatography plate, and fluorescence can be observed by naked eye under ultraviolet lamp. And in 10 mol / L KOH solution environment, no hydrolysis product is detected within 72 h.

[0099] Example 5

[0100] A kind of battery leakage detection method based on riboflavin derivative, in the embodiment, the main component of electrolyte is organic solvent, to enhance the solubility of riboflavin derivative in the system, esterification reaction needs to be carried out on the hydroxyl group on the side chain of riboflavin molecule, specific steps are as follows:

[0101] 500 mL, 1 mol / L riboflavin dichloromethane solution is configured.

[0102] 2.05 mol triethylamine is added to the solution, 2 mol acetyl chloride is slowly added under ice bath condition, after dropwise addition is completed, reaction is carried out for 6 h under anhydrous drying, 0 DEG C, and reaction progress is monitored by thin layer chromatography during reaction.

[0103] After the reaction is completed, the triethylamine hydrochloride generated in the system is filtered out, and an appropriate amount of silica gel is added to the solution. The dichloromethane in the system is removed by rotary evaporation to obtain a dry powder mixture of the reaction product and silica gel.

[0104] The mixed powder is laid on the upper part of the silica gel column, and column chromatography is performed with an eluent of petroleum ether: ethyl acetate = 100:1 to obtain the first eluted part of the product from the column.

[0105] The eluent is rotary evaporated to obtain a light yellow acetic esterified riboflavin derivative, and the reaction yield is 70%.

[0106] The riboflavin molecule modified by the above method is added to the zinc-manganese battery electrolyte, and the concentration is controlled at 0.1 mmol / L. A small amount of solution is dropped on a thin layer chromatography plate, and fluorescence can be observed with the naked eye under ultraviolet light. In the dimethyl carbonate solution environment, the solubility of the esterified derivative is increased from 0.5 g / 100 mL to 5.2 g / 100 mL compared with unmodified riboflavin. Therefore, fluorescence can be detected at low concentrations, and the solubility of the modified molecule in organic solvents is significantly improved.

[0107] Example 6

[0108] A battery leakage detection method based on riboflavin derivatives, in this embodiment, the main component of the electrolyte is an organic solvent. In order to enhance the solubility of riboflavin derivatives in the system, the hydroxyl group on the side chain of riboflavin molecule needs to be esterified. The specific steps are as follows:

[0109] Prepare a 500 mL, 1 mol / L riboflavin ethyl acetate solution.

[0110] Add 2.05 mol of triethylamine to the solution, and slowly add 2 mol of propionyl chloride under ice bath conditions. After the addition is completed, dry under anhydrous conditions at 0°C for 12 hours. The reaction progress is monitored by thin layer chromatography during the reaction.

[0111] After the reaction is completed, the triethylamine hydrochloride generated in the system is filtered out, and an appropriate amount of silica gel is added to the solution. The dichloromethane in the system is removed by rotary evaporation to obtain a dry powder mixture of the reaction product and silica gel.

[0112] The mixed powder is laid on the upper part of the silica gel column, and column chromatography is performed with an eluent of petroleum ether: ethyl acetate = 80:1 to obtain the first eluted part of the product from the column.

[0113] The eluent is rotary evaporated to obtain a light yellow acetic esterified riboflavin derivative, and the reaction yield is 70%.

[0114] The above method modified riboflavin molecules are added to zinc manganese battery electrolyte, control its concentration is 0.1mmol / L, take a small amount of solution drop on thin layer chromatography plate, under UV light can be observed to the naked eye fluorescence. And in the environment of ethylene carbonate solution, the solubility of esterified derivative is improved from 0.4g / 100mL to 4.7g / 100mL.

[0115] Example 7

[0116] In this embodiment, the main component of the electrolyte is sulfuric acid solution of lead-acid battery, the hydroxyl group of riboflavin molecule needs to be halogenated to prevent etherification in the electrolyte and cause property change.

[0117] The specific steps are:

[0118] Prepare 500mL, 1mol / L riboflavin isopropyl ether solution.

[0119] Add 2.04mol triethylamine to the solution, slowly add 0.68mol phosphorus trichloride under ice bath condition, after the completion of dropwise addition, react for 6h under ice water bath environment, and the whole reaction process is protected by argon without water and oxygen. The reaction progress is monitored by thin layer chromatography.

[0120] After the reaction is completed, the triethylamine phosphite generated in the system is filtered out, and an appropriate amount of silica gel is added to the solution. The isopropyl ether solvent in the system is removed by rotary evaporation to obtain a mixture of dry powder reaction product and silica gel.

[0121] The mixed powder is laid on the upper part of the silica gel column, and petroleum ether:dichlorobenzene=10:1 eluent is used for column chromatography separation to obtain the product with the smallest polarity and the first eluted from the chromatographic column.

[0122] After rotary evaporation of the eluent, light yellow chlorinated riboflavin derivative is obtained, and the reaction yield is 72%.

[0123] The above method modified riboflavin molecules are added to lead-acid battery electrolyte, control its concentration is 1mmol / L, take a small amount of solution drop on thin layer chromatography plate, under UV light can be observed to the naked eye fluorescence. And in the environment of 5mol / L H2SO4 solution, no ether compound is detected within 72h.

[0124] Example 8

[0125] A battery leakage detection method based on riboflavin derivative, in this embodiment, the main component of the electrolyte is sulfuric acid solution of lead-acid battery, the hydroxyl group of riboflavin molecule needs to be halogenated to prevent etherification in the electrolyte and cause property change.

[0126] The specific steps are:

[0127] Prepare 500 mL of 1 mol / L solution of riboflavin in dioxane.

[0128] Add 2.05 mol of triethylamine to the solution, and slowly drop 0.7 mol of phosphorus trichloride under ice bath conditions. After the dropping is completed, react for 10 h under ice water bath environment, and the whole reaction process is protected by argon without water and oxygen. Monitor the reaction progress by thin layer chromatography during the reaction process.

[0129] After the reaction is completed, filter the generated triethylamine phosphite in the system, add appropriate silica gel to the solution, remove the dioxane solvent in the system by rotary evaporation, and obtain a dry powder mixture of the reaction product and silica gel.

[0130] Lay the mixed powder on the upper part of the silica gel column, and perform column chromatography separation with an eluent of petroleum ether:toluene = 5:1, to obtain the first eluted part of the product from the column.

[0131] Obtain an orange yellow chlorinated riboflavin derivative after rotary evaporation of the eluent, and the reaction yield is 70%.

[0132] Add the riboflavin molecule modified by the above method to the electrolyte of a lead acid battery, control the concentration to be 0.5 mmol / L, drop a small amount of solution on a thin layer chromatography plate, and observe the fluorescence under a ultraviolet lamp. No ether compound is detected within 72 h in a 5 mol / L H2SO4 solution environment.

[0133] Example 9

[0134] A battery leakage detection method based on riboflavin derivatives, in this embodiment, the main component of the electrolyte is a zinc-manganese battery of a potassium hydroxide alkaline battery solution, and the imide in the riboflavin molecule needs to be alkylated and protected to prevent its hydrolysis in an alkaline environment and cause changes in properties.

[0135] The specific steps are as follows:

[0136] Prepare 500 mL of 1 mol / L solution of riboflavin in isopropanol.

[0137] Add 0.55 mol of sodium tert-butoxide to the solution, and slowly drop 0.5 mol of chlorinated tert-butane under ice bath conditions. After the dropping is completed, react for 6 h under anhydrous room temperature environment, and monitor the reaction progress by thin layer chromatography during the reaction process.

[0138] After the reaction is completed, add a small amount of boric acid to remove the remaining base in the system, and filter the generated sodium chloride in the system. Add appropriate silica gel to the solution, remove the isopropanol solvent in the system by rotary evaporation, and obtain a dry powder mixture of the reaction product and silica gel.

[0139] The mixed powder was laid on the upper part of the silica gel column, and column chromatography was performed with petroleum ether: ethyl acetate = 50:1 range of eluent to obtain the first eluted part of the product from the column.

[0140] The eluent was rotary evaporated to obtain a light yellow tert-butyl-substituted riboflavin derivative, and the reaction yield was 79%.

[0141] The riboflavin molecule modified by the above method was added to the electrolyte of the alkaline zinc-manganese battery, and the concentration was controlled at 0.1 mmol / L. A small amount of solution was dropped on the thin layer chromatography plate, and fluorescence could be observed with the naked eye under the ultraviolet lamp. And in the 10 mol / L KOH solution environment, no hydrolysis product was detected within 72 h.

[0142] Example 10

[0143] A battery leakage detection method based on riboflavin derivatives, in this embodiment, the main component of the electrolyte is lithium hexafluorophosphate battery of potassium hydroxide alkaline battery solution, and the imide in the riboflavin molecule needs to be alkylated to prevent its hydrolysis in alkaline environment and cause changes in properties.

[0144] The specific steps are as follows:

[0145] Prepare 500 mL of 1 mol / L riboflavin propanol solution.

[0146] Add 0.55 mol of potassium tert-butoxide to the solution, and slowly add 0.5 mol of chloro-n-butane under ice bath conditions. After the addition is completed, react for 6 h at room temperature in a water-free environment. The reaction progress was monitored by thin layer chromatography during the reaction.

[0147] After the reaction is completed, a small amount of boric acid is added to remove the remaining base in the system, and the generated potassium chloride in the system is filtered out. An appropriate amount of silica gel is added to the solution, and the propanol solvent in the system is removed by rotary evaporation to obtain a dry powder mixture of the reaction product and silica gel.

[0148] The mixed powder was laid on the upper part of the silica gel column, and column chromatography was performed with petroleum ether: ethyl acetate = 50:1 range of eluent to obtain the first eluted part of the product from the column.

[0149] The eluent was rotary evaporated to obtain a light yellow tert-butyl-substituted riboflavin derivative, and the reaction yield was 79%.

[0150] The riboflavin molecule modified by the above method was added to the electrolyte of the lithium hexafluorophosphate battery, and the concentration was controlled at 0.1 mmol / L. A small amount of solution was dropped on the thin layer chromatography plate, and fluorescence could be observed with the naked eye under the ultraviolet lamp. And in the 10 mol / L KOH solution environment, no hydrolysis product was detected within 72 h.

[0151] Example 11

[0152] A battery leakage detection method based on a riboflavin derivative, in this embodiment, the main component of the electrolyte is an organic solvent, in order to enhance the solubility of the riboflavin derivative in the system, the hydroxyl group on the side chain of the riboflavin molecule needs to be esterified.

[0153] The specific steps are:

[0154] Prepare 500 mL of a 1 mol / L riboflavin chloroform solution.

[0155] Add 2.05 mol of triethylamine to the solution, slowly add 2 mol of propionyl chloride under ice bath conditions, after the addition is complete, dry under anhydrous conditions, and react at 0°C for 6 h. During the reaction process, the progress of the reaction is monitored by thin layer chromatography.

[0156] After the reaction is completed, the generated triethylamine hydrochloride in the system is filtered out, an appropriate amount of silica gel is added to the solution, and the chloroform in the system is removed by rotary evaporation to obtain a dry powder mixture of the reaction product and silica gel.

[0157] Spread the mixed powder on the upper part of the silica gel column, and perform column chromatography separation with an eluent of petroleum ether: ethyl acetate = 80:1 to obtain the first eluted part of the product from the column.

[0158] After rotary evaporation of the eluent, a light yellow propionylated riboflavin derivative is obtained, and the reaction yield is 70%.

[0159] The riboflavin molecule modified by the above method is added to the zinc-manganese battery electrolyte, and the concentration is controlled at 0.1 mmol / L. A small amount of solution is dropped on a thin layer chromatography plate, and fluorescence can be observed with the naked eye under ultraviolet light. In the dimethyl carbonate solution environment, the solubility of the esterified derivative is increased from 0.5 g / 100 mL to 5.5 g / 100 mL compared with unmodified riboflavin.

[0160] Example 12

[0161] A battery leakage detection method based on a riboflavin derivative, in this embodiment, the main component of the electrolyte is an organic solvent, in order to enhance the solubility of the riboflavin derivative in the system, the hydroxyl group on the side chain of the riboflavin molecule needs to be esterified.

[0162] The specific steps are:

[0163] Prepare 500 mL of a 1 mol / L riboflavin methyl acetate solution.

[0164] Add 2.05 mol of triethylamine to the solution, slowly add 2 mol of propionyl chloride under ice bath conditions, after the addition is complete, dry under anhydrous conditions, and react at 0°C for 12 h. During the reaction process, the progress of the reaction is monitored by thin layer chromatography.

[0165] After the reaction is completed, the triethylamine hydrochloride generated in the system is filtered out, and an appropriate amount of silica gel is added to the solution. The ethyl acetate in the system is removed by rotary evaporation to obtain a dry powder mixture of the reaction product and silica gel.

[0166] The mixed powder is laid on the upper part of the silica gel column, and column chromatography separation is performed with an eluent of petroleum ether: ethyl acetate = 80:1 to obtain the first eluted part of the product from the column.

[0167] After the eluent is rotary evaporated, a light yellow propionic acid esterified riboflavin derivative is obtained, and the reaction yield is 61%.

[0168] The riboflavin molecule modified by the above method is added to the electrolyte of a zinc-manganese battery, and the concentration is controlled at 0.1 mmol / L. A small amount of solution is dropped on a thin layer chromatography plate, and fluorescence can be observed with the naked eye under ultraviolet light. In the environment of ethylene carbonate solution, the solubility of the esterified derivative is increased from 0.4 g / 100 mL to 3.7 g / 100 mL compared with unmodified riboflavin.

[0169] Example 13

[0170] In this embodiment, the main component of the electrolyte of the lead-acid battery is sulfuric acid solution, and the hydroxyl group in the riboflavin molecule needs to be halogenated to prevent etherification in the electrolyte and cause changes in properties.

[0171] The specific steps are as follows:

[0172] Prepare a 500 mL, 1 mol / L riboflavin methyl tert-butyl ether solution.

[0173] Add 2.04 mol of triethylamine to the solution, and slowly add 0.67 mol of phosphorus tribromide under ice bath conditions. After the addition is completed, react for 12 h under ice water bath environment, and the whole reaction process is protected by argon gas without water and oxygen. The progress of the reaction is monitored by thin layer chromatography.

[0174] After the reaction is completed, the triethylamine phosphite generated in the system is filtered out, and an appropriate amount of silica gel is added to the solution. The methyl tert-butyl ether solvent in the system is removed by rotary evaporation to obtain a dry powder mixture of the reaction product and silica gel.

[0175] The mixed powder is laid on the upper part of the silica gel column, and column chromatography separation is performed with an eluent of petroleum ether: methylbenzene = 20:1 to obtain the product with the smallest polarity, which is the first eluted product from the chromatographic column.

[0176] After the eluent is rotary evaporated, a light yellow propionic acid esterified riboflavin derivative is obtained, and the reaction yield is 61%.

[0177] The above method modified riboflavin molecules are added to the lead-acid battery electrolyte, control its concentration is 1mmol / L, take a small amount of solution drop on thin layer chromatography plate, under the ultraviolet lamp can be observed to the naked eye fluorescence. And in 5mol / L H2SO4 solution environment, 72h no ether compounds are detected to generate.

[0178] Example 14

[0179] A kind of battery leakage detection method based on riboflavin derivative, in this embodiment, the main component of electrolyte is sulfuric acid solution of lead-acid battery, need to be halogenated to protect the hydroxyl group in riboflavin molecule, prevent its etherification in electrolyte causes property change.

[0180] Specific steps are:

[0181] Configuration 500mL, 1mol / L riboflavin methyl ethyl ether solution.

[0182] In the solution, add 2.04mol triethylamine, slowly drop 0.67mol phosphorus trichloride under ice bath condition, after drop completion, react 6h under ice water bath environment, and the whole reaction process is protected by argon without water and oxygen, the reaction progress is monitored by thin layer chromatography during the reaction.

[0183] After the reaction is completed, the triethylamine phosphite generated in the system is filtered out, and an appropriate amount of silica gel is added to the solution. The methyl ethyl ether solvent in the system is removed by rotary evaporation to obtain a dry powder mixture of the reaction product and silica gel.

[0184] The mixed powder is laid on the upper part of the silica gel column, and the eluent of petroleum ether: toluene = 20:1 is used for column chromatography separation to obtain the first eluted part of the product from the column.

[0185] The eluent is rotary evaporated to obtain white chlorinated riboflavin derivative, the reaction yield is 70%.

[0186] The above method modified riboflavin molecules are added to the lead-acid battery electrolyte, control its concentration is 0.5mmol / L, take a small amount of solution drop on thin layer chromatography plate, under the ultraviolet lamp can be observed to the naked eye fluorescence. And in 5mol / L H2SO4 solution environment, 72h no ether compounds are detected to generate.

[0187] Example 15

[0188] A kind of battery leakage detection method based on riboflavin derivative, in this embodiment, the main component of electrolyte is potassium hydroxide alkaline battery solution of zinc-manganese battery, need to be alkylated to protect the imide in riboflavin molecule, prevent its hydrolysis in alkaline environment causes property change.

[0189] Specific steps are:

[0190] Prepare 500 mL of 1 mol / L solution of riboflavin in n-pentanol.

[0191] Add 0.55 mol of sodium tert-butoxide to the solution, and slowly drop 0.5 mol of chloro-tert-butane under ice bath condition. After the dropping is completed, react for 6 h at room temperature in a water-free environment. Monitor the progress of the reaction by thin layer chromatography during the reaction.

[0192] After the reaction is completed, add a small amount of boric acid to remove the residual base in the system, and then filter out the generated sodium chloride in the system. Add an appropriate amount of silica gel to the solution, and remove the n-pentanol solvent in the system by rotary evaporation to obtain a dry powder mixture of the reaction product and silica gel.

[0193] Lay the mixed powder on the upper part of a silica gel column, and perform column chromatography separation with an eluent of petroleum ether: ethyl acetate = 35:1 to obtain the first eluted part of the product from the column.

[0194] After rotary evaporation of the eluent, a white tert-butyl-substituted riboflavin derivative is obtained, and the reaction yield is 78%.

[0195] The riboflavin molecule modified by the above method is added to the electrolyte of an alkaline zinc-manganese battery, and the concentration is controlled to be 0.1 mmol / L. A small amount of solution is dropped on a thin layer chromatography plate, and fluorescence can be observed with the naked eye under a UV lamp. No hydrolysis product is detected within 72 h in a 10 mol / L KOH solution environment.

[0196] Example 16

[0197] A battery leakage detection method based on a riboflavin derivative. In this embodiment, the main component of the electrolyte is lithium hexafluorophosphate battery of potassium hydroxide alkaline battery solution. The imide in the riboflavin molecule needs to be alkylated and protected to prevent its hydrolysis in an alkaline environment and cause changes in properties.

[0198] The specific steps are as follows:

[0199] Prepare 500 mL of 1 mol / L solution of riboflavin in tert-butanol.

[0200] Add 0.56 mol of potassium tert-butoxide to the solution, and slowly drop 0.5 mol of chloro-n-butane under ice bath condition. After the dropping is completed, react for 6 h at room temperature in a water-free environment. Monitor the progress of the reaction by thin layer chromatography during the reaction.

[0201] After the reaction is completed, add a small amount of boric acid to remove the residual base in the system, and then filter out the generated potassium chloride in the system. Add an appropriate amount of silica gel to the solution, and remove the tert-butanol solvent in the system by rotary evaporation to obtain a dry powder mixture of the reaction product and silica gel.

[0202] The mixed powder was spread on the upper part of the silica gel column, and column chromatography was performed with petroleum ether: ethyl acetate = 70:1 range of eluent to obtain the first eluted part of the product from the column.

[0203] The yellowish tert-butyl-substituted riboflavin derivative was obtained after rotary evaporation of the eluent, and the reaction yield was 75%.

[0204] The riboflavin molecule modified by the above method was added to a lithium hexafluorophosphate battery electrolyte, and the concentration was controlled at 0.1 mmol / L. A small amount of solution was dropped on a thin layer chromatography plate, and fluorescence could be observed with the naked eye under ultraviolet light. And in the 10 mol / L KOH solution environment, no hydrolysis product was detected within 72 h.

[0205] Comparative Example 1

[0206] The riboflavin chloro compound in Example 1 and riboflavin were added to two groups of 5 mol / L sulfuric acid solution respectively, and sealed at room temperature.

[0207] After 72 h, yellow granular precipitate appeared in the sulfuric acid solution of riboflavin, and a small amount of solution was taken and dropped on a thin layer chromatography plate, and no fluorescence was observed with the naked eye under ultraviolet light; the sulfuric acid solution of riboflavin chloro compound remained clear, and a small amount of solution was taken and dropped on a thin layer chromatography plate, and fluorescence was observed.

[0208] Comparative Example 2

[0209] The riboflavin butylated derivative in Example 3 and riboflavin were added to two groups of 10 mol / L potassium hydroxide solution respectively, and sealed at room temperature.

[0210] After 72 h, yellow flocculent insoluble matter appeared in the potassium hydroxide solution of riboflavin, and a small amount of solution was taken and dropped on a thin layer chromatography plate, and the fluorescence signal was very weak under ultraviolet light; the potassium hydroxide solution of riboflavin butylated derivative remained clear, and a small amount of solution was taken and dropped on a thin layer chromatography plate, and fluorescence was observed.

[0211] Comparing Example and Comparative Examples 1 and 2, it can be seen that:

[0212] The riboflavin molecule modified by butylation can remain stable in acidic and alkaline environments and retain fluorescence characteristics; however, the unmodified riboflavin molecule is destroyed under acidic and alkaline conditions, the decomposition products are complex, the system cannot maintain a solution form, affecting the quality of the electrolyte and losing the fluorescence characteristics.

[0213] In the description of the present specification, unless otherwise explicitly specified and limited, the terms "mounting", "connection", "connection" and the like should be broadly understood.

[0214] In the description of the specification, the description of the terms "one embodiment", "some embodiments", "exemplary embodiment", "example", "specific example" or "some examples" etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the specification, the exemplary description of the above terms does not necessarily mean the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0215] Of course, the above description is not a limitation of the present application, and the present application is not limited to the above examples. Changes, modifications, additions or substitutions made by those skilled in the art within the spirit of the present application should also be within the scope of the present application.

Claims

1. A method of battery leak detection based on a riboflavin derivative, characterized in that, In the preparation of electrolyte battery, the riboflavin is modified and purified, and the riboflavin derivative is selectively added in the electrolyte, so that it remains stable in nature and has fluorescence activity when added to the electrolyte of acid or alkali or organic solvent, and has good solubility with the electrolyte; when detecting, the surface of the battery is irradiated by using ultraviolet lamp, and the battery electrolyte leakage can be quickly batch detected by naked eye observation.

2. A method of battery leak detection based on a riboflavin derivative according to claim 1, wherein, The modification method of the riboflavin includes halogenation, alkylation or esterification to ensure that the target molecule is stable under the condition of acid or alkali or organic solvent.

3. A method of battery leak detection based on a riboflavin derivative according to claim 2, wherein, For the acid battery with sulfuric acid solution as the electrolyte component, the hydroxyl group in the riboflavin molecule is halogenated to protect it, and the specific steps are as follows: (1) dissolve the riboflavin in anhydrous ether solvent, then add triethylamine; (2) slowly add an appropriate amount of phosphorus trichloride or phosphorus tribromide under ice bath condition, after the addition is completed, react for 6-12h under ice water bath environment, the whole reaction process must be carried out under inert gas protection, and the reaction progress is monitored by thin layer chromatography during the reaction; (3) after the reaction is completed, filter out the triethylamine phosphite generated in the system, add silica gel in the solution, remove the ether solvent in the system by rotary evaporation, and obtain a dry powder mixture of the reaction product and silica gel; (4) lay the mixed powder on the upper part of the silica gel column, and separate the product by column chromatography with eluent, so as to obtain the product part with the smallest polarity and eluted from the chromatographic column first; After the eluent is evaporated by rotary evaporation, the halogenated riboflavin derivative with light yellow or dark yellow color is obtained.

4. A method of battery leak detection based on a riboflavin derivative according to claim 3, wherein, The anhydrous ether solvent includes ethyl ether, propyl ether, isopropyl ether, methyl tert-butyl ether, anisole, tetrahydrofuran or dioxane, and the concentration range is 0.01-2mol / L; the ratio of triethylamine to riboflavin is greater than 4:

1.

5. A method of battery leak detection based on a riboflavin derivative according to claim 3, wherein, The ratio of phosphorus trichloride or phosphorus tribromide to riboflavin is greater than 1.4:

1.

6. A method of battery leak detection based on a riboflavin derivative according to claim 3, wherein, The eluent is a mixture of petroleum ether and toluene, and the volume ratio of toluene to petroleum ether is 1:5-20.

7. A method of battery leak detection based on a riboflavin derivative according to claim 2, wherein, For the alkaline battery with potassium hydroxide solution as the electrolyte component, the imide in the riboflavin molecule is alkylated to protect it, and the specific steps are as follows: (1) dissolve the riboflavin in a protic solvent, add 1-1.1 equivalent of strong base in the solution system, and stir at room temperature; (2) after the base is completely dissolved, slowly add 1-1.1 equivalent of monohalogenated alkane to the solution, after the addition of halogenated alkane is completed, stir for 6-12h under normal temperature and pressure, and the reaction progress is monitored by thin layer chromatography during the reaction; (3) after the reaction is completed, add a weak acid to neutralize the excess base, and then filter out the inorganic salt generated in the reaction; (4) add silica gel to the reaction solution, remove the protic solvent in the system by rotary evaporation, and obtain a dry powder mixture of the reaction product and silica gel; (5) lay the mixed powder on the upper part of the silica gel column, and separate the product by column chromatography with eluent, so as to obtain the product part with the smallest polarity and eluted from the chromatographic column first; (6) after the eluent is evaporated by rotary evaporation, the alkyl-protected riboflavin derivative with white or light yellow color is obtained.

8. A method of battery leak detection based on a riboflavin derivative according to claim 7, wherein, The protic solvent includes methanol, ethanol, propanol, butanol, isobutanol or tert-butanol, and the concentration range is 0.05-2mol / L.

9. A method of battery leak detection based on a riboflavin derivative according to claim 7, wherein, The strong base includes lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, sodium ethoxide, potassium ethoxide or potassium tert-butoxide.

10. A method of battery leak detection based on a riboflavin derivative according to claim 7, wherein, The monohalogenated alkane includes bromoethane, bromopropane, n-butyl chloride, chlorinated tert-butane, brominated tert-butane, chlorinated cyclopentane or brominated cyclopentane.

11. A method of battery leak detection based on a riboflavin derivative according to claim 7, wherein, The eluent is a mixture of petroleum ether and ethyl acetate, and the volume ratio of ethyl acetate to petroleum ether is 1:10-50.

12. A method of battery leak detection based on a riboflavin derivative according to claim 2, wherein, For the lithium ion battery with the electrolyte solvent component being an organic solvent of ethylene carbonate, propylene carbonate, chain dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate, an esterification reaction is carried out on the hydroxyl group on the side chain of the riboflavin molecule, and the specific steps are as follows: (1) The riboflavin is dissolved in an organic solvent, and then triethylamine is added; (2) Acetyl chloride is slowly and appropriately added under ice bath conditions, and after the addition is completed, the reaction is carried out for 6-12 hours under an ice water bath environment, and the whole reaction process is carried out under anhydrous drying, and the reaction progress is monitored by thin layer chromatography during the reaction process; (3) After the reaction is completed, the generated triethylamine hydrochloride in the system is filtered out; (4) Silica gel is added to the solution, and ether solvents in the system are removed by rotary evaporation to obtain a dry powder mixture of the reaction product and silica gel; (5) The mixed powder is laid on the upper part of a silica gel column, and an eluent with a volume ratio of petroleum ether to ethyl acetate in the range of 5-100:1 is used for column chromatography separation to obtain the product part eluted first from the chromatographic column; (6) The eluent is evaporated by rotary evaporation to obtain a light yellow esterified riboflavin derivative.

13. A method of battery leak detection based on a riboflavin derivative according to claim 12, wherein, The organic solvent is a non-alcohol solvent stable under acidic conditions, including dichloromethane, ethyl acetate, toluene, xylene, diethyl ether, tetrahydrofuran or dioxane, with a concentration range of 0.01-2 mol / L; the ratio of triethylamine to riboflavin is greater than 4:1, the ratio of acetyl chloride to riboflavin is greater than 4:1, and the amount of acetyl chloride is less than that of triethylamine.

14. A method of battery leak detection based on a riboflavin derivative according to claim 12, wherein, The eluent is a mixture of petroleum ether and ethyl acetate, and the volume ratio of ethyl acetate to petroleum ether is 1:5-100.

15. The riboflavin derivative-based battery leakage detection method according to any one of claims 1-14 is applied to the leakage detection of batteries using electrolytes, including lithium batteries, lead-acid batteries, cadmium-nickel batteries, nickel-hydrogen batteries, zinc-silver batteries, alkaline zinc-manganese batteries or acid zinc-manganese batteries, and can also be applied to the detection of battery packs.

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