CN115728427A - Acid value determination method for photovoltaic adhesive film and auxiliary materials - Google Patents
Acid value determination method for photovoltaic adhesive film and auxiliary materials Download PDFInfo
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- 239000002253 acid Substances 0.000 title claims abstract description 108
- 239000002313 adhesive film Substances 0.000 title claims abstract description 79
- 239000000463 material Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 101
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000004806 packaging method and process Methods 0.000 claims abstract description 41
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000007791 liquid phase Substances 0.000 claims abstract description 29
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 29
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 238000012360 testing method Methods 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000002791 soaking Methods 0.000 claims abstract description 16
- 238000004458 analytical method Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 claims abstract 7
- 238000004090 dissolution Methods 0.000 claims abstract 2
- 239000000523 sample Substances 0.000 claims description 133
- 238000001556 precipitation Methods 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 230000032683 aging Effects 0.000 claims description 20
- 238000004445 quantitative analysis Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000010030 laminating Methods 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 7
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 238000001819 mass spectrum Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 239000012488 sample solution Substances 0.000 claims description 2
- 238000004448 titration Methods 0.000 claims description 2
- 238000004949 mass spectrometry Methods 0.000 abstract description 25
- 239000000126 substance Substances 0.000 abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 41
- 239000000243 solution Substances 0.000 description 23
- 239000011148 porous material Substances 0.000 description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 230000002431 foraging effect Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000009545 invasion Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 101100406487 Drosophila melanogaster Or47a gene Proteins 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention relates to the field of photovoltaic cell packaging adhesive films, in particular to a method for measuring acid values of a photovoltaic adhesive film and auxiliary materials; the determination method comprises the following steps: preparing a sample to be detected; and (3) testing: respectively placing the samples to be detected in appointed solvents for ultrasonic soaking to dissolve acid precipitates in the samples in the solvents, and respectively marking the concentration C of the precipitates of various solvents x Soaking the solution with the highest acid dissolution concentration in the sample solvent, respectively mixing the solution with acetonitrile, n-hexane, n-heptane and isopropanol according to a proportion, filtering by a filter press valve, taking the filtered liquid, and quantitatively analyzing by liquid phase mass spectrometry LC-MS to obtain the mass of the acid content in the sample, wherein the mass is recorded as AN x (ii) a Analyzing a test result; comparing the acid content in the solvent in the step 5, selecting the sample with the highest acid content to be respectively mixed with acetonitrile, n-hexane, n-heptane, isopropanol and the like, and firstlyThe analysis of the substance and content of the acid in the solution is carried out by using liquid phase mass spectrometry (LC-MS) innovatively.
Description
Technical Field
The invention relates to the field of photovoltaic cell packaging adhesive films, in particular to a method for measuring acid values of a photovoltaic adhesive film and auxiliary materials.
Background
The packaging adhesive film in the photovoltaic module plays a crucial role in the power generation life of the module, and the quality of the packaging adhesive film plays a key role in the protection of the module. In the prior art, after an EVA/EP packaging adhesive film (containing EVA raw materials, acidic auxiliary materials, and the like) is aged for a long time at high temperature and high humidity, after water vapor invades, EVA colloidal particle molecular chains and auxiliaries in the adhesive film are easily subjected to water degradation, and acetic acid, acid-containing organic matters, dibasic acid or polybasic acid and the like are released. Acetic acid and acid-containing organic matters generated after hydrolysis can corrode slurry, welding strips and the like on the surfaces of the battery pieces, and the power generation power and the service life of the assembly are further influenced. At present, researches on hydrolysis of the packaging adhesive film and corrosion of the battery are only limited to changes of power attenuation of the assembly and light and shade in an EL photo of the assembly, and quantitative data on corrosion changes of the adhesive film under different hydrolysis degrees and changes of micromolecular acetic acid or acid organic matters in the adhesive film are not available. The analysis of the acid-base property and the hydrolysis substance of the adhesive film only stays in the acid-base neutralization aspect, so that the release and the quantification of acetic acid and acid organic matters in the EVA/EP adhesive film are monitored and characterized together by using the combination of various evaluation means, and a basis and a reference are provided for the formula design of the packaging adhesive film and the selection of auxiliary materials.
Disclosure of Invention
The purpose of the invention is: the method for measuring the acid values of the photovoltaic adhesive film and the auxiliary materials is provided, the release and quantification of acetic acid and acid organic matters in the EVA/EP adhesive film are monitored and represented, and basis and reference are provided for the formula design of the packaging adhesive film and the selection of the auxiliary materials.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for measuring acid values of a photovoltaic adhesive film and auxiliary materials comprises the following steps:
preparing a sample to be detected;
and (3) testing: respectively placing the samples to be detected in appointed solvents for ultrasonic soaking to dissolve acid precipitates in the samples in the solvents, and respectively marking the concentration C of the precipitates of various solvents x X represents the quantity of the solvent, the solution with the highest acid dissolving concentration in the solvent of the soaked sample,respectively mixing the extract with acetonitrile, n-hexane, n-heptane and isopropanol according to a proportion, filtering by a filter press valve, and taking the filtered liquid, and performing liquid phase mass spectrometry (LC-MS) quantitative analysis to obtain the mass of the acid content in the sample, wherein the mass is recorded as AN x ；
And (6) analyzing a test result.
Further, the packaging adhesive film and the auxiliary materials are polymers containing ethylene-vinyl acetate copolymers and blends thereof in raw materials; the sample quality of the glue film sample, the auxiliary material sample and the raw film sample is controlled to be between 10 and 30 g.
Further, the preparation of the sample piece of the sample to be tested specifically includes: (1) laminating packaging adhesive films to be used as samples to be detected, (2) laminating the packaging adhesive films to prepare sample pieces, stripping each layer of packaging adhesive films to be used as samples to be detected after high-temperature damp-heat aging treatment, (3) packaging the extruded and granulated polymer particles by using a water-permeable gas sample bag, then carrying out high-temperature damp-heat aging, and using the particles before and after aging treatment as samples to be detected, (4) using an auxiliary agent as the samples to be detected.
Furthermore, the sample piece is obtained by laminating glass, a first adhesive film, a second adhesive film and a cover plate which are sequentially laminated, and the size of the packaging adhesive film is larger than or equal to that of the glass.
Further, the temperature of the high-temperature moist heat aging treatment is 100 to 125 ℃, and the humidity is 95 to 100 percent RH;
the ultrasonic frequency of the ultrasonic soaking is 40-60kHZ, the time is 25-45, the ultrasonic frequency is preferably 60kHZ, the ultrasonic time is preferably 30min, and the aperture of the filter-pressing valve is 1 μm.
Further, the specified solvents include:
solvent 1: mixing ethanol and methanol according to a ratio of 1,
solvent 2: ethanol and toluene were mixed at 1:1, solvent 3: ethanol, methanol and water are mixed according to a ratio of 1.5,
solvent 4: water, xylene, toluene and ethanol were mixed in a 1.5,
solvent 5: ethanol, xylene, toluene and methanol were mixed at a ratio of 1.5;
the amount of each solvent is 200-300ml.
Further, the mixing ratio of the solution with the highest acid-soluble concentration in the solvent for soaking the sample to acetonitrile, n-hexane, n-heptane and isopropanol is 1.5, 1:2, 2:1, 1:3 and 1:1 respectively.
Further, the concentration of the eluate C x As determined by a chemi-potentiometric titration with base titration, by the formula C = a 1 ×(V 1 -V 0 )×56.10/M Y Calculating to obtain the C value; wherein, a 1 Denotes the concentration of alkali solution, V, required for neutralizing the acid in the eluate 1 Denotes the volume of the neutralized educt, V 0 Denotes the volume, M, required for the neutralization of a particular solvent with the titrating base Y Represents the weight of the sample to be tested.
Further, in the acid value determination method, a sample injection liquid is subjected to liquid phase mass spectrometry (LC-MS) test, and the acid content accounts for the mass AN of the sample by comparing the reaction signal time and the peak area ratio of each substance x By the formula AN = C × V m ×{[S Y -(S x -S 0 )]/S Y }/M Y Calculating to obtain; wherein C represents a measured value of an amount of an acid released in the sample solution, and V m Represents the volume of the eluate entering the liquid phase mass spectrometer LC-MS, S Y Represents the total area of the peak of the eluate in LC-MS, S x Represents the peak area of the acid in the eluate in a specific solvent in LC-MS, S 0 Denotes the area of the peak of a particular solvent in LC-MS, M Y Represents the weight of the sample to be tested.
When the acid value determination method of the invention obtains the AN value of the acid content in the adhesive film to be tested through liquid phase mass spectrometry (LC-MS) test, the leaching treatment comprises the following steps: putting the glue film to be tested into a closed container, adding the solvent into the closed container, pressing the glue film to be tested below the liquid level of the closed container by using a polypropylene filter screen, and then heating the closed container in a water bath; preferably, the solvent is one or more of deionized water, distilled water or ultrapure water.
Further, the analysis of the test result specifically includes:
C x the numerical value indicates that the precipitation degree of the adhesive film and the auxiliary materials in a specific solvent system is larger before and after the wet heat aging,
AN x the numerical value represents the acid content of the adhesive film and the auxiliary materials before and after the wet heat aging;
C x and AN x When the numerical value keeps a lower state, the probability that the sample to be detected generates acid and releases the acid is lower, and the photovoltaic module and the battery can be better protected when the packaging adhesive film and the auxiliary materials are selected.
The technical scheme adopted by the invention has the beneficial effects that:
generally, after long-term aging and water vapor invasion, the packaging adhesive film is easy to degrade molecular chains of the adhesive film to release a part of acid. Meanwhile, part of the organic additives added to the packaging adhesive film may also decompose part of the acidic substances after aging. These acidic materials (including acid decomposed from the adhesive film itself and/or acid generated from aging decomposition of some additives, such as one or more of acetic acid, phenol, carbonic acid or silanol) can react with slurry, grid lines, solder strips and the like on the surface of the battery piece under the strong action of water vapor, and finally show corrosion on the EL photo, and also influence the generated power of the assembly. Based on the steps, the conditions of acid release and precipitation of the packaging adhesive film for the photovoltaic module and auxiliary materials contained in the adhesive film in an extreme damp and hot environment are simulated, the release content (namely C1-5) of acid in certain specific solvents generated in practical application (after aging under long-term high-temperature conditions and water vapor invasion) of the packaging adhesive film is accurately and reliably obtained, the sample with the highest acid content is selected to be respectively mixed with acetonitrile, normal hexane, normal heptane, isopropanol and the like by comparing the acid content in the solvent in 5, and the substance and the content of the acid in the solution are analyzed by innovatively using a liquid phase mass spectrum (LC-MS) for the first time. By analyzing the content and the type of the acid in the specific solution and combining the corrosion condition of the sample assembly in the EL, the degree of potential failure risk of the photovoltaic packaging adhesive film caused by the type and the content of the auxiliary agent in the sample is estimated. The test evaluation method has higher test efficiency, and the test result has instructive on the judgment of the packaging adhesive film and has higher evaluation reliability.
Detailed Description
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in other embodiments according to the disclosure of the present invention, or make simple changes or modifications on the design structure and idea of the present invention, and fall into the protection scope of the present invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
Example 1
A sample preparation stage: directly taking the packaging adhesive film as a raw film sample to be detected, wherein the mass of the sample is 12g;
and (3) a testing stage: placing a sample to be detected in 200ml of solvents 1-5, mixing the sample with 5 solvents respectively, soaking the sample in the solvent, performing ultrasonic treatment for 30min to precipitate acid in the sample, dissolving the acid in the solvent, and obtaining the concentration C of the embodiment through a calculation formula of the concentration of a precipitation solution of the solvent 1-5 In which C is 3 Compared with other solvents with the highest release amount, the solution of the sample precipitated in the solvent 3 is selected as an analysis sample, and is respectively mixed with acetonitrile, n-hexane, n-heptane and isopropanol according to (1.5, 1:2, 2:1 and 1:1), and the liquid filtered by a filter press valve with a pore diameter of 1 μm is used for quantitative analysis of liquid phase mass spectrometry (LC-MS).
The mass of the acid content in the sample after the filtrate is analyzed and quantitatively analyzed by liquid phase mass spectrometry (LC-MS) is recorded as AN 1-5 (ppm), the solution of the sample after solvent 3 precipitation was found to have a higher precipitation concentration in isopropanol of 1:1. Concentration C of the precipitation liquid in this example 3 The value is 0.09647mg (KOH)/g, and the ratio AN of the acid content in the educt to the mass of the sample 4 At 98.91ppm, the acid in the eluate was the major component of free radical acrylic acid.
Example 2
A sample preparation stage: laminating the packaging adhesive film to be used as a sample to be detected, wherein the mass of the sample is 10g;
and (3) a testing stage: placing the sample to be tested in 200ml of solvent 1-5, mixing with 5 solvents respectively, soaking the sample in the solvent, and performing ultrasonic treatment for 30min to obtain the sampleThe acid precipitate is dissolved in the solvent, and the concentration of the example is recorded as C by the calculation formula of the concentration of the precipitate of the solvent 1-5 In which C is 4 Compared with other solvents with the highest release amount, the solution of the sample precipitated in the solvent 4 is selected as an analysis sample, and is respectively mixed with acetonitrile, n-hexane, n-heptane and isopropanol according to (1.5, 1:2, 2:1 and 1:1), and the liquid filtered by a filter press valve with a pore diameter of 1 μm is used for quantitative analysis of liquid phase mass spectrometry (LC-MS).
The mass of the acid content in the sample after the filtrate is analyzed and quantitatively analyzed by liquid phase mass spectrometry (LC-MS) is recorded as AN 1-5 (ppm), the solution of the sample precipitated in solvent 4 was found to have a high precipitation concentration in 1:2 in n-hexane. Concentration C of the precipitation liquid in this example 4 The value is 0.01358mg (KOH)/g, and the ratio AN of the acid content in the educt to the mass of the sample 2 At 14.56ppm, the acid in the eluate was the major component free radical acrylic acid.
Example 3
A sample preparation stage: laminating the packaging adhesive film, placing the laminated packaging adhesive film in an aging environment with the temperature of 110 ℃ and the humidity of 100% for aging for 96 hours, and taking the aged adhesive film as a sample to be tested, wherein the mass of the sample is 15g;
and (3) a testing stage: placing a sample to be detected in 200ml of solvents 1-5, mixing the sample with 5 solvents respectively, soaking the sample in the solvent for 30min by ultrasonic treatment to precipitate acid in the sample and dissolve the acid in the solvent, and obtaining the concentration C of the embodiment by a precipitation solution concentration calculation formula of the solvent 1-5 In which C is 2 Compared with other solvents with the highest release amount, the solution of the sample precipitated in the solvent 2 is selected as an analysis sample, and is respectively mixed with acetonitrile, n-hexane, n-heptane and isopropanol according to (1.5, 1:2, 2:1 and 1:1), and the liquid filtered by a filter press valve with a pore diameter of 1 μm is used for quantitative analysis of liquid phase mass spectrometry (LC-MS).
The mass of the acid content in the sample after the filtrate is analyzed and quantitatively analyzed by liquid phase mass spectrometry (LC-MS) is recorded as AN 1-5 (ppm), the solution of the sample after solvent 2 precipitation was found to have a higher precipitation concentration in n-heptane 2:1. Concentration C of the precipitation liquid in this example 2 The value is 0.1683mg (KOH)/g, acid in the eluateThe proportion of the content in the sample mass AN 3 182.31ppm, and the main components of the acid in the eluate are acetic acid, free radical acrylic acid, phosphorous acid, etc.
Example 4
A sample preparation stage: taking the auxiliary material colloidal particles as a sample to be detected, wherein the mass of the sample is 15g;
and (3) a testing stage: placing a sample to be detected in 200ml of solvents 1-5, mixing the sample with 5 solvents respectively, soaking the sample in the solvent, performing ultrasonic treatment for 30min to precipitate acid in the sample, dissolving the acid in the solvent, and obtaining the concentration C of the embodiment through a calculation formula of the concentration of a precipitation solution of the solvent 1-5 In which C is 2 Compared with other solvents with the highest release amount, the solution of the sample precipitated in the solvent 1 is selected as an analysis sample, and is respectively mixed with acetonitrile, n-hexane, n-heptane and isopropanol according to (1.5, 1:2, 2:1 and 1:1), and the liquid filtered by a filter press valve with a pore diameter of 1 μm is used for quantitative analysis of liquid phase mass spectrometry (LC-MS).
The mass of the acid content in the sample after the filtrate is analyzed and quantitatively analyzed by liquid phase mass spectrometry (LC-MS) is recorded as AN 1-5 (ppm), the solution of the sample after solvent 3 was found to have a higher precipitation concentration in 2:1 n-heptane. Concentration C of the precipitation liquid in this example 1 The numerical value is 0.6835mg (KOH)/g, and the acid content in the precipitation liquid accounts for the mass ratio AN of the sample 3 703.34ppm, and the main components of the acid in the eluate are phosphorous acid, free radical acrylic acid, acetic acid, etc.
Example 5
A sample preparation stage: taking the auxiliary material colloidal particles as a sample to be detected, wherein the mass of the sample is 30g;
and (3) a testing stage: placing a sample to be detected in 200ml of solvents 1-5, mixing the sample with 5 solvents respectively, soaking the sample in the solvent for 30min by ultrasonic treatment to precipitate acid in the sample and dissolve the acid in the solvent, and obtaining the concentration C of the embodiment by a precipitation solution concentration calculation formula of the solvent 1-5 In which C is 4 Compared with other solvents with the highest release amount, the solution of the sample precipitated in the solvent 2 is selected as an analysis sample, mixed with acetonitrile, n-hexane, n-heptane and isopropanol according to (1.5, 1:2, 2:1 and 1:1), and subjected to pressure passing through a 1 μm apertureThe liquid filtered by the filter valve is used for quantitative analysis of liquid phase mass spectrometry (LC-MS). The mass of the acid content in the sample after the filtrate is analyzed and quantitatively analyzed by liquid phase mass spectrometry (LC-MS) is recorded as AN 1-5 (ppm), the solution of the sample after solvent 4 precipitation was found to have a higher precipitation concentration in isopropanol of 1:1. Concentration C of the precipitation liquid in this example 1 The value is 1.3253mg (KOH)/g, and the ratio AN of the acid content in the educt to the mass of the sample 4 1483.52ppm, and the main components of the acid in the eluate are phosphorous acid, free radical acrylic acid, acetic acid, etc.
Comparative example 1
A sample preparation stage: laminating the packaging adhesive film, placing the laminated packaging adhesive film in an aging environment with the temperature of 125 ℃ and the humidity of 85% for aging for 192 hours, and taking the aged adhesive film as a sample to be tested, wherein the mass of the sample is 5g;
and (3) a testing stage: placing a sample to be tested in 200ml of a solvent 6, mixing ethanol, xylene, toluene and methanol according to the solvent proportion according to 1.5 6 (ii) a The eluate was mixed with n-hexane (3:1), and the liquid after filtration through a filter press valve with a pore size of 1 μm was used for quantitative analysis by liquid phase mass spectrometry (LC-MS). The mass of the acid content in the sample after the quantitative analysis by liquid phase mass spectrometry (LC-MS) is recorded as AN 6 (ppm). Concentration C of the precipitation liquid in this example 6 The value is 0.1857mg (KOH)/g, and the ratio AN of the acid content in the educt to the mass of the sample 6 196.63ppm, and the main components of acid in the eluate are acetic acid and free radical acrylic acid.
Comparative example 2
A sample preparation stage: laminating the packaging adhesive film, placing the packaging adhesive film in an aging environment with 85 ℃ and 85% humidity for aging for 1000h, and taking the aged adhesive film as a sample to be tested, wherein the sample mass is 15g;
and (3) a testing stage: placing a sample to be tested in 200ml of a solvent 7, mixing the solvent with water, xylene, toluene and ethanol according to the ratio of 1.5The concentration of the example is marked as C 7 (ii) a The eluate was mixed with acetonitrile (3:1) and the liquid after filtration through a filter press valve with a pore size of 1 μm was used for quantitative analysis by liquid phase mass spectrometry (LC-MS). The mass of the acid content in the sample after the quantitative analysis by liquid phase mass spectrometry (LC-MS) is recorded as AN 7 (ppm). Concentration C of the precipitation liquid in this example 7 The value is 0.3423mg (KOH)/g, and the ratio AN of the acid content in the educt to the mass of the sample 7 356.67ppm, and the main components of the acid in the eluate are acetic acid, free radical acrylic acid, phosphorous acid, etc.
Comparative example 3
A sample preparation stage: laminating the packaging adhesive film to be used as a raw film sample to be detected, wherein the sample mass is 12g;
and (3) a testing stage: placing a sample to be detected in 200ml of a solvent 8, mixing ethanol and water according to a solvent ratio of 1.5, soaking the sample in the solvent for 10min by ultrasonic treatment to precipitate acid in the sample and dissolve the acid in the solvent, and obtaining the concentration of the embodiment through a calculation formula of the concentration of a precipitation solution of the solvent and recording the concentration as C 8 (ii) a The eluate was mixed with n-hexane (3:1), and the liquid after filtration through a filter press valve with a pore size of 1 μm was used for quantitative analysis by liquid phase mass spectrometry (LC-MS). The mass of the acid content in the sample after the quantitative analysis by liquid phase mass spectrometry (LC-MS) is recorded as AN 8 (ppm). Concentration C of the precipitation liquid in this example 8 The value is 0.02045mg (KOH)/g, and the ratio AN of the acid content in the educt to the mass of the sample 8 At 22.61ppm, the main component of the acid in the eluate was acetic acid.
Comparative example 4
A sample preparation stage: laminating the packaging adhesive film, placing the packaging adhesive film in an aging environment at 150 ℃ for aging for 1000h, and taking the aged adhesive film as a sample to be tested, wherein the mass of the sample is 10g;
and (3) a testing stage: placing a sample to be detected in 250ml of solvent 1, wherein the solvent is pure water, soaking the sample in the solvent for ultrasonic treatment for 60min to precipitate acid in the sample and dissolve the acid in the solvent, and obtaining the concentration of the embodiment through a precipitation liquid concentration calculation formula of the solvent and recording the concentration as C 9 (ii) a The eluate was mixed with n-heptane (3:1) and the liquid after filtration through a filter press valve with a pore size of 1 μm was used for quantitative analysis by liquid phase mass spectrometry (LC-MS). The acid content of the sample after quantitative analysis by liquid phase mass spectrometry (LC-MS)Quality of (A) is recorded as AN 9 (ppm). Concentration C of the precipitation liquid in this example 9 The value is 0.1282mg (KOH)/g, the ratio of the acid content in the educt to the sample mass is 138.43ppm, and the main component of the acid in the educt is acetic acid.
Comparative example 5
A sample preparation stage: laminating the packaging adhesive film to be used as a sample to be detected, wherein the sample mass is 50g;
and (3) a testing stage: placing a sample to be tested in 200ml of solvent 1, mixing ethanol and toluene according to the proportion of 1:3, soaking the sample in the solvent for ultrasonic treatment for 25min to precipitate acid in the sample and dissolve the acid in the solvent, and obtaining the concentration of the embodiment through a precipitation liquid concentration calculation formula of the solvent and recording the concentration as C 10 (ii) a The eluate was mixed with n-heptane (1:1) and the liquid after filtration through a filter press valve with a pore size of 1 μm was used for quantitative analysis by liquid phase mass spectrometry (LC-MS). The mass of the acid content in the sample after quantitative analysis by liquid phase mass spectrometry (LC-MS) was designated as AN10 (ppm). Concentration C of the precipitation liquid in this example 10 The value is 0.3423mg (KOH)/g, the ratio of the acid content in the educt to the sample mass is 357.38ppm, and the main components of the acid in the educt are free radical acrylic acid, acetic acid, silicic acid and the like.
By comparing the acid precipitation amount and the proportion of the acid content in the sample mass of different embodiments, the method is found to be capable of evaluating the corrosion of the photovoltaic packaging on the component and the battery piece more accurately, screening the acid values of the adhesive film, the auxiliary material and the auxiliary agent rapidly, and providing a reference for the improvement and promotion of the follow-up photovoltaic adhesive film formula.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A method for measuring acid values of photovoltaic adhesive films and auxiliary materials is characterized by comprising the following steps: the determination method comprises the following steps:
preparing a sample to be detected;
and (3) testing: respectively placing the samples to be detected in appointed solvents for ultrasonic soaking to dissolve acid precipitates in the samples in the solvents, and respectively marking the concentration C of the precipitates of various solvents x X represents the quantity of the solvent, the solution with the highest acid dissolving concentration in the solvent of the soaked sample is mixed with acetonitrile, n-hexane, n-heptane and isopropanol according to the proportion respectively, a filter press valve is used for filtering, the mass of the acid content in the sample after the filtered liquid is subjected to liquid phase mass spectrum LC-MS quantitative analysis is recorded as AN x ；
And (6) analyzing a test result.
2. The method for measuring the acid value of the photovoltaic adhesive film and the auxiliary material according to claim 1, wherein the method comprises the following steps: the packaging adhesive film and the auxiliary materials are polymers containing ethylene-vinyl acetate copolymer and blends thereof; the sample quality of the glue film sample, the auxiliary material sample and the raw film sample is controlled to be between 10 and 30 g.
3. The method for measuring the acid value of the photovoltaic adhesive film and the auxiliary material according to claim 2, wherein the method comprises the following steps: the preparation of the sample piece of the sample to be detected specifically comprises the following steps: (1) laminating packaging adhesive films to be used as samples to be detected, (2) laminating the packaging adhesive films to prepare sample pieces, stripping each layer of packaging adhesive films to be used as samples to be detected after high-temperature damp-heat aging treatment, (3) packaging the extruded and granulated polymer particles by using a water-permeable gas sample bag, then carrying out high-temperature damp-heat aging, and using the particles before and after aging treatment as samples to be detected, (4) using an auxiliary agent as the samples to be detected.
4. The method for measuring the acid value of the photovoltaic adhesive film and the auxiliary material as claimed in claim 3, wherein the method comprises the following steps: the sample piece is obtained by laminating glass, a first adhesive film, a second adhesive film and a cover plate which are sequentially laminated, wherein the size of the packaging adhesive film is larger than or equal to that of the glass.
5. The method for measuring the acid value of the photovoltaic adhesive film and the auxiliary material according to claim 3, wherein the method comprises the following steps: the temperature of the high-temperature damp-heat aging treatment is 100-125 ℃, and the humidity is 95-100 percent RH;
the ultrasonic frequency of the ultrasonic soaking is 40-60kHZ, the time is 25-45, the ultrasonic frequency is preferably 60kHZ, the ultrasonic time is preferably 30min, and the aperture of the filter-pressing valve is 1 μm.
6. The method for measuring the acid value of the photovoltaic adhesive film and the auxiliary material as claimed in claim 1, wherein the method comprises the following steps: the specified solvents include:
solvent 1: mixing ethanol and methanol according to a ratio of 1,
solvent 2: mixing ethanol and toluene according to 1:1,
solvent 3: ethanol, methanol and water are mixed according to a ratio of 1.5,
solvent 4: water, xylene, toluene and ethanol were mixed in a 1.5,
solvent 5: ethanol, xylene, toluene and methanol were mixed as 1.5;
the amount of each solvent is 200-300ml.
7. The method for measuring the acid value of the photovoltaic adhesive film and the auxiliary material as claimed in claim 1, wherein the method comprises the following steps: the mixing ratio of the solution with the highest acid dissolution concentration in the soaking sample solvent to acetonitrile, n-hexane, n-heptane and isopropanol is 1.5, 1:2, 2:1, 1:3 and 1:1 respectively.
8. The method for measuring the acid value of the photovoltaic adhesive film and the auxiliary material according to claim 1, wherein the method comprises the following steps: concentration of the eluate C x Determination by a chemi-potentiostat for base titration by the formula C = a 1 ×(V 1 -V 0 )×56.10/M Y Calculating to obtain the C value; wherein, a 1 Denotes the concentration of alkali solution, V, required for neutralizing the acid in the eluate 1 Denotes the volume of the neutralized educt, V 0 Represents the volume, M, required for neutralization of a particular solvent with a titrating base Y Represents the weight of the sample to be tested.
9. According to the rightThe method for measuring the acid values of the photovoltaic adhesive film and the auxiliary materials, according to claim 1, is characterized in that: acid content in sample mass AN x By the formula AN = CxV m ×{[S Y -(S x -S 0 )]/S Y }/M Y Calculating to obtain; wherein C represents a measured value of an amount of an acid released in the sample solution, and V m Represents the volume of the eluate entering the liquid phase mass spectrometer LC-MS, S Y Represents the total area of the peak of the eluate in LC-MS, S x Represents the peak area of the acid in the eluate in a specific solvent in LC-MS, S 0 Denotes the area of the peak of a particular solvent in LC-MS, M Y Represents the weight of the sample to be tested.
10. The method for measuring the acid value of the photovoltaic adhesive film and the auxiliary material according to claim 1, wherein the method comprises the following steps: the test result analysis specifically comprises:
C x the value of the adhesive film and the auxiliary materials represents that the precipitation degree of the adhesive film and the auxiliary materials in a specific solvent system is larger before and after the wet heat aging,
AN x the numerical value represents the acid content of the adhesive film and the auxiliary materials before and after the wet heat aging;
C x and AN x When the numerical value keeps a lower state, the probability that the sample to be detected generates acid and releases the acid is lower, and the photovoltaic module and the battery can be better protected when the packaging adhesive film and the auxiliary materials are selected.
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