CN114591374A - A compound and its synthesis method, and a method for detecting hydrogen ion concentration in a lithium battery - Google Patents
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 31
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- 238000000034 method Methods 0.000 title claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 13
- 238000001308 synthesis method Methods 0.000 title abstract 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 36
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000004440 column chromatography Methods 0.000 claims abstract description 8
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- 238000010992 reflux Methods 0.000 claims abstract description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 55
- 239000000243 solution Substances 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 29
- 239000012086 standard solution Substances 0.000 claims description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
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- 238000010189 synthetic method Methods 0.000 claims description 5
- 230000005526 G1 to G0 transition Effects 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
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- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 238000013375 chromatographic separation Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 239000011255 nonaqueous electrolyte Substances 0.000 description 6
- HLYRMDDXFDINCB-UHFFFAOYSA-N carbon monoxide;iron Chemical group [Fe].[Fe].[Fe].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] HLYRMDDXFDINCB-UHFFFAOYSA-N 0.000 description 5
- 108010020056 Hydrogenase Proteins 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002424 x-ray crystallography Methods 0.000 description 2
- 241000203069 Archaea Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 241000206602 Eukaryota Species 0.000 description 1
- 229910002548 FeFe Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 238000004082 amperometric method Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004662 dithiols Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
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Abstract
本发明公开了一种化合物及其合成方法，其结构式为
Description
技术领域technical field
本发明涉及锂电池检测领域，具体涉及一种化合物及其合成方法、检测锂电池中氢离子浓度的方法。The invention relates to the field of lithium battery detection, in particular to a compound and a method for synthesizing it, and a method for detecting the concentration of hydrogen ions in a lithium battery.
背景技术Background technique
如今，锂离子电池在我们生活中得到广泛的应用，其应用领域包括手机、电脑、电动工具等，随着智能的生活用品的应用越来越广泛，未来的智能生活用品也将是应用锂离子电池的重大领域,因此锂离子电池的各项指标测试尤为重要。Today, lithium-ion batteries are widely used in our lives, and their application fields include mobile phones, computers, power tools, etc. As the application of smart daily necessities becomes more and more extensive, the future smart daily necessities will also use lithium-ion batteries. Therefore, the test of various indicators of lithium-ion batteries is particularly important.
锂离子电池非水电解液成分包括氢氟酸，锂离子电池用的非水电解液中微量的氢氟酸对电池的容量、循环寿命和安全性都有很大影响，因此在锂电池电解液的生产、储存、运输以及电池的制造过程中必须对氢氟酸的含量进行严格的监控。目前对非水体系中氟化氢的测定主要采用BTB作指示剂，通过目测的方法判断终点，会给指示剂法带来较大的误差。The non-aqueous electrolyte components of lithium-ion batteries include hydrofluoric acid. The trace amount of hydrofluoric acid in the non-aqueous electrolyte for lithium-ion batteries has a great impact on the capacity, cycle life and safety of the battery. The content of hydrofluoric acid must be strictly monitored during the production, storage, transportation and manufacturing of batteries. At present, BTB is mainly used as indicator for the determination of hydrogen fluoride in non-aqueous systems, and the end point is judged by visual inspection, which will bring large errors to the indicator method.
自然界某些细菌、古菌和真核生物中存在一种能够催化质子还原释放氢气和氢气氧化的金属酶，被称为氢化酶。由于化合物[Fe2(CO)6(μ-SR)2]与[FeFe]-氢化酶活性中心的结构具有高度的相似性，研究中发现这类化合物也能够催化质子还原释放氢气。In some bacteria, archaea and eukaryotes in nature, there is a metalloenzyme that can catalyze the reduction of protons to release hydrogen and hydrogen oxidation, which is called hydrogenase. Due to the high structural similarity between the compound [Fe 2 (CO) 6 (μ-SR) 2 ] and the active center of [FeFe]-hydrogenase, it was found that this compound can also catalyze proton reduction to release hydrogen.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于至少解决现有技术中存在的技术问题之一，提供一种检测锂电池中氢离子浓度的新方法。本发明合成了含碱基吡啶功能团的[2Fe2S]核氢化酶模型化合物1{Fe2(CO)5[(μ-SCH2)2C(CH3)(2-Py)]}，以其为催化剂，利用电化学循环伏安分析测定在锂离子电池非水电解液中氢离子浓度。The purpose of the present invention is to solve at least one of the technical problems existing in the prior art, and to provide a new method for detecting the hydrogen ion concentration in a lithium battery. In the present invention, a [2Fe2S] nuclear hydrogenase model compound 1{Fe 2 (CO) 5 [(μ-SCH 2 ) 2 C(CH 3 )(2-Py)]} containing a base pyridine functional group is synthesized, and its As a catalyst, the concentration of hydrogen ions in the non-aqueous electrolyte of lithium ion batteries was measured by electrochemical cyclic voltammetry.
本发明的技术解决方案如下：The technical solution of the present invention is as follows:
一种化合物，其结构式如下：A compound whose structural formula is as follows:
上述的化合物的合成方法，包括以下步骤：The synthetic method of above-mentioned compound, comprises the following steps:
(1)在Ar保护下，将十二羰基三铁溶解于甲苯中，然后加入含有2-甲基-2-丙基联吡啶-1,3-二硫醇的甲苯溶液中，加热回流反应3.5～4.5h，减压下除去溶剂，得到残渣；(1) Under the protection of Ar, the dodecacarbonyl triiron is dissolved in toluene, and then added to the toluene solution containing 2-methyl-2-propyl bipyridine-1,3-dithiol, and the reaction is heated under reflux for 3.5 ~4.5h, the solvent was removed under reduced pressure to obtain a residue;
(2)将残渣用柱色谱分离，收集得到暗绿色溶液，对暗绿色溶液进行减压除去溶剂，得到深绿色固体；(2) the residue is separated by column chromatography, collected to obtain a dark green solution, and the dark green solution is removed under reduced pressure to remove the solvent to obtain a dark green solid;
(3)将深绿色固体溶于乙腈，过滤除去不溶物，减压下除去部分溶液，置于-15～-25℃下冷冻1～3天，得暗绿色晶体。(3) Dissolve the dark green solid in acetonitrile, filter to remove insoluble matter, remove part of the solution under reduced pressure, and freeze at -15 to -25°C for 1 to 3 days to obtain dark green crystals.
本发明的具体实施方式中，所述步骤(1)中，在Ar保护下，将0.35～0.45mmol十二羰基三铁溶解于4～6ml干燥甲苯中，然后加入8～12ml含有2-甲基-2-丙基联吡啶-1,3-二硫醇的甲苯溶液中，加热至105～115℃，回流反应3.5～4.5h。In a specific embodiment of the present invention, in the step (1), under the protection of Ar, 0.35-0.45 mmol of triiron dodecacarbonyl is dissolved in 4-6 ml of dry toluene, and then 8-12 ml of 2-methyl -2-propylbipyridine-1,3-dithiol in toluene solution, heated to 105～115°C, and reacted under reflux for 3.5～4.5h.
本发明的具体实施方式中，所述步骤(1)中，将0.4mmol十二羰基三铁溶解于5ml干燥甲苯中，然后加入10ml含有2-甲基-2-丙基联吡啶-1,3-二硫醇的甲苯溶液中，加热至110℃，回流反应4h。In a specific embodiment of the present invention, in the step (1), 0.4 mmol of triiron dodecacarbonyl was dissolved in 5 ml of dry toluene, and then 10 ml of 2-methyl-2-propyl bipyridine-1,3 -The toluene solution of dithiol was heated to 110°C, and the reaction was refluxed for 4h.
本发明的具体实施方式中，所述步骤(2)中，柱色谱分离的展开剂为体积比为4:1的正己烷:乙酸乙酯的混合液，固定相是硅胶。In a specific embodiment of the present invention, in the step (2), the developing agent of the column chromatography separation is a mixed solution of n-hexane:ethyl acetate with a volume ratio of 4:1, and the stationary phase is silica gel.
本发明的具体实施方式中，所述步骤(3)中，置于-20℃下冷冻2天。In a specific embodiment of the present invention, in the step (3), it is placed at -20°C and frozen for 2 days.
采用上述的化合物检测锂电池中氢离子浓度的方法，包括以下步骤：The method for detecting hydrogen ion concentration in a lithium battery using the above-mentioned compound comprises the following steps:
S1、配制含不同浓度氢氟酸的电解液标准溶液，并在标准溶液中加入权利要求1所述的化合物，对各标准溶液分别进行电化学循环伏安扫描，分别得到各标准溶液的循环伏安曲线，将氢氟酸的浓度与循环伏安曲线峰值电流值对应点作图，得到氢氟酸的浓度与电流强度之间的线性方程；S1, prepare electrolyte standard solutions containing different concentrations of hydrofluoric acid, and add the compound according to
S2、配制待测试液，并在待测试液中加入权利要求1所述的化合物，对待测试液进行电化学循环伏安扫描，得到待测试液的循环伏安曲线，将待测试液的循环伏安曲线峰值电流值代入标准溶液的线性方程中，即可计算出待测试液中氢氟酸的浓度。S2, prepare the liquid to be tested, add the compound according to
本发明的具体实施方式中，在标准溶液和待测试液中分别加入3～5mmol上述的化合物。In a specific embodiment of the present invention, 3-5 mmol of the above-mentioned compounds are respectively added to the standard solution and the solution to be tested.
本发明的具体实施方式中，步骤S1中，氢氟酸的浓度与电流强度之间线性方程为y＝8.23x+14.1，其中，x为氢氟酸的浓度，y为电流强度。In a specific embodiment of the present invention, in step S1, the linear equation between the concentration of hydrofluoric acid and the current intensity is y=8.23x+14.1, where x is the concentration of hydrofluoric acid, and y is the current intensity.
本发明至少具有以下有益效果之一：The present invention has at least one of the following beneficial effects:
本发明通过合成了一种含碱基吡啶功能团的[2Fe2S]核氢化酶模型化合物{Fe2(CO)5[(μ-SCH2)2C(CH3)(2-Py)]}，该化合物能够催化质子还原，从而以该化合物为催化剂，可以催化锂电池中质子(即氢氟酸)还原，利用电化学循环伏安法测试含有HF的标准溶液的循环伏安曲线，将HF的浓度与循环伏安曲线峰值电流值对应点作图，得到线性方程，峰值电流与HF浓度呈较好的线性关系，R2为99.6％，最低检测限为0.3mM；然后再利用电化学循环伏安法测试待测溶液的的循环伏安曲线，将待测溶液的峰值电流代入线性方程，即可计算出待测溶液中的检测值。本发明的检测方法简单方便、准确性高。The present invention has synthesized a [2Fe2S] nuclear hydrogenase model compound {Fe 2 (CO) 5 [(μ-SCH 2 ) 2 C(CH 3 )(2-Py)]} containing a basic pyridine functional group, The compound can catalyze the reduction of protons, so that the compound can be used as a catalyst to catalyze the reduction of protons (ie, hydrofluoric acid) in lithium batteries. The cyclic voltammetry curve of a standard solution containing HF is tested by electrochemical cyclic voltammetry. The concentration and the corresponding point of the peak current value of the cyclic voltammetry curve were plotted, and a linear equation was obtained. The peak current had a good linear relationship with the HF concentration, R 2 was 99.6%, and the minimum detection limit was 0.3mM; The cyclic voltammetry curve of the solution to be tested is tested by amperometric method, and the peak current of the solution to be tested is substituted into the linear equation to calculate the detection value in the solution to be tested. The detection method of the invention is simple, convenient and high in accuracy.
附图说明Description of drawings
图1为实施例1中各标准溶液的循环伏安曲线图；Fig. 1 is the cyclic voltammogram of each standard solution in
图2为实施例1中标准溶液中氢氟酸的浓度与电流强度线性关系图。2 is a linear relationship diagram of the concentration of hydrofluoric acid in the standard solution in Example 1 and the current intensity.
具体实施方式Detailed ways
一种用于检测锂电池中氢离子浓度的化合物的合成方法，包括以下步骤：A method for synthesizing a compound for detecting hydrogen ion concentration in a lithium battery, comprising the following steps:
(1)在Ar保护下，将0.35～0.45mmol十二羰基三铁溶解于4～6ml干燥甲苯中，然后加入8～12ml含有0.4mmol(0.079g)2-甲基-2-丙基联吡啶-1,3-二硫醇的甲苯溶液中，加热至105～115℃，回流反应3.5～4.5h，减压下除去溶剂，得到残渣；优选地，将0.4mmol十二羰基三铁溶解于5ml干燥甲苯中，然后加入10ml含有2-甲基-2-丙基联吡啶-1,3-二硫醇的甲苯溶液中，加热至110℃，回流反应4h，减压下除去溶剂，得到残渣。(1) Under the protection of Ar, dissolve 0.35-0.45 mmol of triiron dodecacarbonyl in 4-6 ml of dry toluene, then add 8-12 ml of 2-methyl-2-propyl bipyridine containing 0.4 mmol (0.079 g) -1,3-dithiol in toluene solution, heated to 105～115°C, refluxed for 3.5～4.5h, and the solvent was removed under reduced pressure to obtain a residue; preferably, 0.4mmol of triiron dodecacarbonyl was dissolved in 5ml Dry the toluene, then add 10 ml of a toluene solution containing 2-methyl-2-propyl bipyridine-1,3-dithiol, heat to 110 °C, reflux for 4 h, remove the solvent under reduced pressure, and obtain a residue.
(2)将残渣用柱色谱分离，收集得到暗绿色溶液，对暗绿色溶液进行减压除去溶剂，得到深绿色固体。其中，柱色谱分离的展开剂为体积比为4:1的正己烷:乙酸乙酯的混合液，固定相是硅胶。(2) The residue was separated by column chromatography to obtain a dark green solution, and the dark green solution was removed under reduced pressure to obtain a dark green solid. Wherein, the developing agent of the column chromatography separation is a mixed solution of n-hexane:ethyl acetate with a volume ratio of 4:1, and the stationary phase is silica gel.
(3)将深绿色固体溶于5ml乙腈，过滤除去不溶物，减压下除去部分溶液，置于-15～-25℃下冷冻1～3天，优选地，置于-20℃下冷冻2天，得暗绿色晶体，利用元素分析法和X射线晶体衍射技术分析该晶体的成分，推测出该晶体为含碱基吡啶功能团的[2Fe2S]核氢化酶模型化合物{Fe2(CO)5[(μ-SCH2)2C(CH3)(2-Py)]}，其结构式如下所示：(3) Dissolve the dark green solid in 5ml of acetonitrile, filter to remove insoluble matter, remove part of the solution under reduced pressure, and freeze at -15 to -25°C for 1 to 3 days, preferably, freeze at -20°C for 2 Days, dark green crystals were obtained. The composition of the crystals was analyzed by elemental analysis and X-ray crystallography, and it was inferred that the crystals were model compounds of [2Fe2S] nuclear hydrogenase containing basic pyridine functional groups {Fe 2 (CO) 5 ] [(μ-SCH 2 ) 2 C(CH 3 )(2-Py)]}, its structural formula is as follows:
以上述化合物为催化剂，利用电化学循环伏安分析测定在锂离子电池非水电解液中氢离子浓度，具体包括以下步骤：Taking the above-mentioned compound as a catalyst, utilizing electrochemical cyclic voltammetry analysis to measure the hydrogen ion concentration in the non-aqueous electrolyte of the lithium ion battery, specifically comprising the following steps:
S1、配制含不同浓度氢氟酸的电解液标准溶液，并在标准溶液加入上述化合物作为催化剂，对各标准溶液分别进行电化学循环伏安扫描，分别得到各标准溶液的循环伏安曲线，将各标准溶液中含有的氢氟酸的浓度(x)与循环伏安曲线峰值电流值(即电流强度y)对应点作图，得到x与y之间的线性方程。S1, prepare electrolyte standard solutions containing different concentrations of hydrofluoric acid, and add the above-mentioned compounds as catalysts to the standard solutions, carry out electrochemical cyclic voltammetry scans on each standard solution respectively, and obtain the cyclic voltammetry curves of each standard solution, respectively. The concentration (x) of hydrofluoric acid contained in each standard solution is plotted against the corresponding point of the peak current value of the cyclic voltammetry curve (ie, the current intensity y), and a linear equation between x and y is obtained.
S2、配制待测试液，并在待测试液加入上述化合物作为催化剂，分别对待测试液进行电化学循环伏安扫描，得到待测试液的循环伏安曲线，将待测试液的循环伏安曲线峰值电流值，即电流强度y代入线性方程中，计算出x值，即可检测出待测试液中的氢离子浓度。S2, prepare the liquid to be tested, and add the above-mentioned compound as a catalyst to the liquid to be tested, perform electrochemical cyclic voltammetry scanning of the liquid to be tested respectively, obtain the cyclic voltammetry curve of the liquid to be tested, and calculate the peak value of the cyclic voltammetry curve of the liquid to be tested The current value, that is, the current intensity y, is substituted into the linear equation, and the x value is calculated to detect the hydrogen ion concentration in the liquid to be tested.
下面用具体实施例对本发明做进一步详细说明，但本发明不仅局限于以下具体实施例。The present invention will be described in further detail below with specific examples, but the present invention is not limited to the following specific examples.
实施例1Example 1
在Ar保护下，将0.4mmol(0.216g)十二羰基三铁溶解于5ml干燥甲苯中，然后加入10ml含有0.4mmol(0.079g)2-甲基-2-丙基联吡啶-1,3-二硫醇的甲苯溶液中，加热至110℃，回流反应4h，减压下除去溶剂，得到残渣；Under the protection of Ar, 0.4 mmol (0.216 g) of triiron dodecacarbonyl was dissolved in 5 ml of dry toluene, and then 10 ml containing 0.4 mmol (0.079 g) of 2-methyl-2-propylbipyridine-1,3- Dithiol in toluene solution, heated to 110 °C, refluxed for 4 h, and the solvent was removed under reduced pressure to obtain a residue;
(2)将残渣用柱色谱分离，收集得到暗绿色溶液，对暗绿色溶液进行减压除去溶剂，得到深绿色固体；其中，柱色谱分离的展开剂为体积比为4:1的正己烷:乙酸乙酯的混合液，固定相是硅胶。(2) the residue is separated by column chromatography, and the dark green solution is collected and obtained, and the dark green solution is decompressed to remove the solvent to obtain a dark green solid; wherein, the developing agent of the column chromatography separation is the n-hexane that the volume ratio is 4:1: A mixture of ethyl acetate, and the stationary phase is silica gel.
(3)将深绿色固体溶于5ml乙腈，过滤除去不溶物，减压下除去部分溶液，置于-20℃下冷冻两天，得暗绿色晶体，利用元素分析法和X射线晶体衍射技术分析该晶体的成分，推测出该晶体的结构如下所示：(3) Dissolve the dark green solid in 5 ml of acetonitrile, filter to remove insoluble matter, remove part of the solution under reduced pressure, and freeze at -20°C for two days to obtain dark green crystals, which are analyzed by elemental analysis and X-ray crystallography. The composition of the crystal, and the structure of the crystal is deduced as follows:
以上述晶体为催化剂，利用电化学循环伏安分析测定在锂离子电池非水电解液中氢离子浓度，具体包括以下步骤：Taking the above-mentioned crystal as a catalyst, utilizing electrochemical cyclic voltammetry analysis to measure the hydrogen ion concentration in the non-aqueous electrolyte of the lithium ion battery, specifically comprising the following steps:
S1、配制氢氟酸标准溶液：称取50.00g锂离子电池(锂盐：LiPF6)的电解液，以400ml碳酸乙烯酯溶剂溶解，定容至1000ml溶液，移取6份150ml溶液于电化学实验池中，分别加入4.0mmol催化剂，其中5份加入不同浓度(1.00mM、2.00mM、3.00mM、4.00mM和5.00mM)的氢氟酸，另一份不加氢氟酸，作为空白对照组，得到不同氢氟酸浓度的标准溶液。S1. Prepare a standard solution of hydrofluoric acid: Weigh 50.00g of the electrolyte of a lithium-ion battery (lithium salt: LiPF 6 ), dissolve it in 400ml of ethylene carbonate solvent, set the volume to 1000ml of solution, pipette 6 parts of 150ml of solution into the battery In the chemical experiment pool, 4.0 mmol catalysts were added respectively, 5 of which were added with hydrofluoric acid of different concentrations (1.00 mM, 2.00 mM, 3.00 mM, 4.00 mM and 5.00 mM), and the other without hydrofluoric acid, as a blank control group to obtain standard solutions with different concentrations of hydrofluoric acid.
制作标准曲线：对各标准溶液分别进行电化学循环伏安扫描，如图1所示，分别得到各溶液的循环伏安曲线。由图1可知，随着HF浓度的增加，循环伏安峰值电流也逐渐增大。Preparation of standard curve: carry out electrochemical cyclic voltammetry scanning of each standard solution, as shown in Figure 1, to obtain the cyclic voltammetry curve of each solution. It can be seen from Figure 1 that with the increase of HF concentration, the peak current of cyclic voltammetry also increases gradually.
然后将氢氟酸的浓度与循环伏安曲线峰值电流值对应点作图，如图2所示，得到氢氟酸的浓度(x)与电流强度(y)的线性关系图，线性方程为y＝8.23x+14.1。由图2可以看出，峰值电流与HF浓度呈较好的线性关系，R2为99.6％，最低检测限为0.3mM，因此该方法可以测试锂离子电池的电解液(非水)中不同氢离子浓度。Then the concentration of hydrofluoric acid and the corresponding point of the peak current value of the cyclic voltammetry curve are plotted, as shown in Figure 2, to obtain a linear relationship between the concentration of hydrofluoric acid (x) and the current intensity (y), the linear equation is y =8.23x+14.1. It can be seen from Figure 2 that the peak current has a good linear relationship with the HF concentration, R 2 is 99.6%, and the minimum detection limit is 0.3 mM, so this method can test different hydrogen in the electrolyte (non-aqueous) of lithium-ion batteries. ion concentration.
S2、配制待测试液：同步骤S1的方法配制待测试液，对待测试液分别编号为1号(氢氟酸浓度0.30mM)、2号(1.00mM)、3号(2.50mM)、4号(4.50mM)、5号(10.00mM)、6号(15.00mM)，分别加入4.0mmol催化剂，对5份待测试液进行电化学循环伏安扫描，得到5份待测试液的循环伏安曲线，将5份待测试液的循环伏安曲线峰值电流值，即电流强度y代入标准溶液的线性方程中，计算出5份待测试液中氢离子浓度，结果如表1所示：S2. Prepare the liquid to be tested: prepare the liquid to be tested in the same way as in step S1. The liquid to be tested is numbered as No. 1 (hydrofluoric acid concentration 0.30 mM), No. 2 (1.00 mM), No. 3 (2.50 mM), and No. 4. (4.50 mM), No. 5 (10.00 mM), No. 6 (15.00 mM), add 4.0 mmol of catalyst respectively, carry out electrochemical cyclic voltammetry scanning on 5 parts to be tested, and obtain the cyclic voltammetry curves of 5 parts to be tested , the peak current value of the cyclic voltammetry curve of 5 parts of the liquid to be tested, that is, the current intensity y, is substituted into the linear equation of the standard solution, and the concentration of hydrogen ions in the 5 parts of the liquid to be tested is calculated, and the results are shown in Table 1:
表1Table 1
由表1可以看出，通过本发明方法得到的1～6号待测试液中氢离子浓度的检测值与氢离子浓度的实际值(氢氟酸浓度)的误差均在5％范围内，由此说明，本发明的方法能够准确的检测锂离子电池非水电解液中氢离子浓度。As can be seen from Table 1, the error between the detected value of the hydrogen ion concentration and the actual value of the hydrogen ion concentration (hydrofluoric acid concentration) in the No. This shows that the method of the present invention can accurately detect the hydrogen ion concentration in the non-aqueous electrolyte of the lithium ion battery.
以上仅是本发明的特征实施范例，对本发明保护范围不构成任何限制。凡采用同等交换或者等效替换而形成的技术方案，均落在本发明权利保护范围之内。The above are only characteristic implementation examples of the present invention, and do not constitute any limitation to the protection scope of the present invention. All technical solutions formed by equivalent exchange or equivalent replacement fall within the protection scope of the present invention.
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