CN113740328B - Method for detecting transition metal dissolution amount of secondary battery electrode material and color developing agent - Google Patents
Method for detecting transition metal dissolution amount of secondary battery electrode material and color developing agent Download PDFInfo
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- CN113740328B CN113740328B CN202110252089.0A CN202110252089A CN113740328B CN 113740328 B CN113740328 B CN 113740328B CN 202110252089 A CN202110252089 A CN 202110252089A CN 113740328 B CN113740328 B CN 113740328B
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 45
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 43
- 238000004090 dissolution Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000007772 electrode material Substances 0.000 title claims abstract description 27
- 239000003792 electrolyte Substances 0.000 claims abstract description 68
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 238000000870 ultraviolet spectroscopy Methods 0.000 claims abstract description 26
- 238000002835 absorbance Methods 0.000 claims abstract description 24
- 238000001514 detection method Methods 0.000 claims abstract description 22
- 238000011088 calibration curve Methods 0.000 claims abstract description 12
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 25
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 19
- 229910052744 lithium Inorganic materials 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 19
- 238000012360 testing method Methods 0.000 claims description 18
- WLNTVTDTBKPTCA-UHFFFAOYSA-N 4-[(5-chloropyridin-2-yl)diazenyl]benzene-1,3-diamine Chemical compound NC1=CC(N)=CC=C1N=NC1=CC=C(Cl)C=N1 WLNTVTDTBKPTCA-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 8
- IOMXCGDXEUDZAK-UHFFFAOYSA-N chembl1511179 Chemical compound OC1=CC=C2C=CC=CC2=C1N=NC1=NC=CS1 IOMXCGDXEUDZAK-UHFFFAOYSA-N 0.000 claims description 8
- 229950011260 betanaphthol Drugs 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- OBFSQMXGZIYMMN-UHFFFAOYSA-N 3-chloro-2-hexadecylpyridine Chemical compound CCCCCCCCCCCCCCCCC1=NC=CC=C1Cl OBFSQMXGZIYMMN-UHFFFAOYSA-N 0.000 claims description 6
- DVBJBNKEBPCGSY-UHFFFAOYSA-M cetylpyridinium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 DVBJBNKEBPCGSY-UHFFFAOYSA-M 0.000 claims description 6
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 6
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 6
- 239000012086 standard solution Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- -1 hexafluorophosphate Chemical compound 0.000 claims description 5
- RJNYNDHYSJRRDW-UHFFFAOYSA-N 4-(pyridin-2-yldiazenyl)benzene-1,3-diol Chemical compound OC1=CC(O)=CC=C1N=NC1=CC=CC=N1 RJNYNDHYSJRRDW-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- LLYOXZQVOKALCD-UHFFFAOYSA-N chembl1400298 Chemical compound OC1=CC=C2C=CC=CC2=C1N=NC1=CC=CC=N1 LLYOXZQVOKALCD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- 229910002001 transition metal nitrate Inorganic materials 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 6
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000003860 storage Methods 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 6
- 230000007704 transition Effects 0.000 description 5
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- HNVCXDAVEHOIBP-UHFFFAOYSA-N 2-[(5-bromopyridin-2-yl)diazenyl]-5-(diethylamino)phenol Chemical compound OC1=CC(N(CC)CC)=CC=C1N=NC1=CC=C(Br)C=N1 HNVCXDAVEHOIBP-UHFFFAOYSA-N 0.000 description 3
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000000624 total reflection X-ray fluorescence spectroscopy Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- FCEOGYWNOSBEPV-FDGPNNRMSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FCEOGYWNOSBEPV-FDGPNNRMSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004471 energy level splitting Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
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Abstract
The invention relates to a method for detecting the dissolution amount of transition metal of a secondary battery electrode material and a color reagent; the detection method comprises the following steps: adding a proper amount of color developing agent into a certain amount of blank electrolyte to prepare an indication electrolyte containing the color developing agent; wherein the color developing agent is pyridine azo organic matters; placing a to-be-detected transition metal oxide electrode plate which is subjected to electrochemical charge and discharge to a set state of charge (SOC) in a cuvette, quantitatively adding an indication electrolyte, adding a blank electrolyte, and regulating the concentration of a color developing agent in the solution to the set concentration to obtain the to-be-detected electrolyte; and storing the cuvette according to the preset temperature and time, performing ultraviolet-visible spectrophotometry on the electrolyte to be detected at a set time node to obtain absorbance, and comparing the absorbance with a calibration curve to obtain the dissolution amount of the transition metal of the secondary battery electrode material.
Description
Technical Field
The invention relates to the technical field of battery material detection, in particular to a method for detecting the dissolution amount of transition metal of a secondary battery electrode material and a color reagent.
Background
With the development of new energy automobiles and various portable electronic devices in new times, secondary batteries are being widely studied and focused as key electrochemical energy storage devices. The study of the failure principle of the secondary battery has important significance for improving the performance of the secondary battery. Among the many failure principles, the problem of transition metal dissolution is one of the main reasons that limit battery cycle life and storage life. Transition metal dissolution is closely related to interface properties of electrode materials and electrolyte, and the transition metal dissolution is often accompanied by problems of surface structure phase change, particle breakage, lattice oxygen loss and the like. Accurate detection of transition metals dissolved in the electrolyte thus facilitates a further understanding of the mechanism by which the transition metals dissolve.
The spectroscopy is a detection method with high sensitivity and no damage, but the methods such as inductively coupled high-frequency plasma atomic emission spectroscopy (ICP), atomic Absorption Spectroscopy (AAS), total reflection X-ray fluorescence spectroscopy (TRXFS) and the like have the problems of long detection flow, long sample pretreatment time and high detection cost to different degrees.
The invention patent application CN110873694A proposes a method for directly detecting transition metal ions in electrolyte by using ultraviolet-visible spectrophotometry (UV-vis), and can detect the transition metal ions relatively quickly and simply.
The transition metal ions are generally present in solvated form in solution and in the form of complexes of solvent molecules in a particular solvent. The geometry formed by the solvent molecule ligand has specific orientation, so that the originally degenerated d orbit of the transition metal is subjected to energy level splitting. According to the crystal field theory, the split energy is divided into two parts, and the valence electron is in a stable ground state when in a low energy level. When external energy is excited, the valence electrons easily absorb energy and transition to a higher energy level, thereby generating an absorption spectrum. The transition is called d-d transition, and the wavelength corresponding to the d-d transition energy is just in the visible light range, so that an absorption peak is generated in the visible light region, and the color is displayed on the outside. Generally, transition metal complexes have their own characteristic absorption peaks, and thus such absorption peaks can be used to detect transition metals. However, the absorbance of the transition is generally not strong and is greatly affected by the solvent, and the direct measurement of the peak of the complex formed by the solvent and the transition metal is not applicable to systems with low dissolution content of some transition metals. In the patent application CN110873694a, the solvent is a commercially and laboratory solvent such as Ethylene Carbonate (EC), dimethyl carbonate (DMC), and other carbonates, ethers, and carboxylic acid esters, and this is a problem.
Therefore, the development and perfection of the UV-vis detection method are necessary, and a rapid transition metal ion detection method suitable for the whole system is established.
Disclosure of Invention
The embodiment of the invention provides a method for detecting the dissolution amount of transition metal in a secondary battery electrode material and a color developing agent, wherein the color developing agent and transition metal ions in electrolyte to be detected form a complex by the aid of the color developing agent, so that the detection sensitivity is improved, and the detection of the dissolution amount of the transition metal in the secondary battery electrode material with wider application range is realized.
In a first aspect, an embodiment of the present invention provides a method for detecting a dissolution amount of a transition metal of an electrode material of a secondary battery, including:
adding a proper amount of color developing agent into a certain amount of blank electrolyte to prepare an indication electrolyte containing the color developing agent; the color developing agent is pyridine azo organic matters;
placing a to-be-detected transition metal oxide electrode plate which is subjected to electrochemical charge and discharge to a set charge state in a cuvette, quantitatively adding an indication electrolyte, and adding a blank electrolyte to adjust the concentration of a color developing agent in the solution to the set concentration to obtain the to-be-detected electrolyte;
and storing the cuvette according to the preset temperature and time, performing ultraviolet-visible spectrophotometry on the electrolyte to be detected at a set time node to obtain absorbance, and comparing the absorbance with a calibration curve to obtain the dissolution amount of the transition metal of the secondary battery electrode material.
Preferably, the color-developing agent specifically includes: one or more of 4- (2-Pyridylazo) resorcinol (4- (2-pyridyzo) restorer, PAR), 1- (2-Pyridylazo) -2-naphthol (1- (2-pyridyzo) -2-naphthol, PAN), 4- (5-Chloro-2-pyridine) -azo-1, 3-diaminobenzene (4- (5-Chloro-2-pyridyzo) -1, 3-phenolediamine, 5-Cl-PADAB), 2- (5-Bromo-2-Pyridylazo) -5- (diethylamino) phenol (2- (5-bromo2-pyridyzo) -5- (diethyl-phenolo, 5-Br-PADAP), 1- (2-Thiazolylazo) -2-naphthol (1- (2-thiazolyzo) -2-naphthol, TAN).
Preferably, the blank electrolyte includes: a solvent and an additive;
wherein the solvent specifically comprises: one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate.
Preferably, the transition metal oxide electrode plate to be measured specifically comprises: an electrode plate of a lithium battery or a sodium battery containing any one of lithium cobaltate, lithium manganate, lithium iron phosphate, ternary material and lithium-rich material;
the transition metal of the secondary battery electrode material specifically comprises transition metal in any one of lithium cobaltate, lithium manganate, lithium iron phosphate, ternary material, lithium-rich material and modified material of the above materials.
Preferably, the SOC is in the range of 0% to 100% and the set concentration of the developer is 50 to 100 (. Times.10) - 6 mol/L), the preset temperature is-20 ℃ to 80 ℃.
Preferably, for the to-be-detected transition metal oxide electrode sheet in a charged state, the detection method further includes: adding a surfactant while quantitatively adding the indication electrolyte;
the surfactant comprises: cetyl trimethylammonium bromide (CTAB), cetyl trimethylammonium chloride (CTAC), cetyl Pyridine Chloride (CPC), cetyl Pyridine Bromide (CPB).
Preferably, the method further comprises:
adding a proper amount of salt containing transition metal ions into a certain amount of blank electrolyte, and preparing a series of standard electrolytes containing the transition metal ions with different concentrations;
UV-vis testing was performed on each standard solution, and a calibration curve of the transition metal ions in the electrolyte was fitted according to the data obtained from the testing.
Further preferably, the transition metal ion-containing salt specifically includes: one or more of transition metal nitrate, perchlorate, acetylacetonate, hexafluorophosphate, bistrifluoromethylsulfonylimine salts;
the standard electrolyte containing transition metal ions with a concentration of 2-100 (x 10) - 6 mol/L), the series of different concentrations comprising at least three different concentrations.
In a second aspect, an embodiment of the present invention provides a developer for detecting a dissolved amount of a transition metal of an electrode material of a secondary battery, the developer being a pyridine azo-based organic compound, including: one or more of 4- (2-Pyridylazo) resorcinol (4- (2-pyridyzo) restorer, PAR), 1- (2-Pyridylazo) -2-naphthol (1- (2-pyridyzo) -2-naphthol, PAN), 4- (5-Chloro-2-pyridine) -azo-1, 3-diaminobenzene (4- (5-Chloro-2-pyridyzo) -1, 3-phenolediamine, 5-Cl-PADAB), 2- (5-Bromo-2-Pyridylazo) -5- (diethylamino) phenol (2- (5-bromo2-pyridyzo) -5- (diethyl-phenolo, 5-Br-PADAP), 1- (2-Thiazolylazo) -2-naphthol (1- (2-thiazolyzo) -2-naphthol, TAN).
Preferably, the color developing agent forms a complex with transition metal ions in the electrolyte to be tested, the absorbance of the complex is tested by ultraviolet-visible spectrophotometry, and the dissolution amount of the transition metal of the secondary battery electrode material is obtained by comparing with a calibration curve.
The invention provides a method for detecting the dissolution amount of transition metal of a secondary battery electrode material by using pyridine azo organic matters as a color developing agent for enhancing color development through ultraviolet-visible spectrophotometry (UV-vis), which complements and perfects the defect of directly testing the content of transition metal ions by using a UV-vis method, and can controllably lead the transition metal to form stable complex, thereby realizing the detection of the transition metal ions. The method adds the color reagent to enhance the UV-vis signal response of trace transition metal elements in the electrolyte, greatly improves the detection limit, can analyze the failure behavior of the transition metal dissolution in the electrodes in different states under the condition of not damaging the electrode plates, can rapidly judge the failure state of the electrodes by measuring the transition metal dissolution quantity of the electrodes under different conditions (such as different temperatures and different charge and discharge states), and can evaluate the stability of certain electrode materials in the electrolyte to a certain extent. In addition, the method provides possibility for subsequent electrochemical tests, so as to develop in-situ tests. The method provided by the invention has the advantages of high speed, high efficiency and accurate detection.
Drawings
The technical scheme of the embodiment of the invention is further described in detail through the drawings and the embodiments.
FIG. 1 is a flow chart of a detection method provided by an embodiment of the invention;
FIG. 2 is a graph of UV-vis spectra of 3 pole pieces provided in example 1 of the present invention at different storage times;
FIG. 3 is a UV-vis spectrum of a series of PAR standard electrolytes with different Co concentrations provided in example 1 of the present invention;
FIG. 4 is a graph showing the absorbance-concentration relationship at 612nm of Co-PAR provided in example 1 of the present invention;
FIG. 5 is a graph of UV-vis spectra of pole pieces 7-40, 7-42 provided in example 2 of the present invention at different storage times;
FIG. 6 is a graph of UV-vis spectra of pole pieces 7-36, 7-39 provided in example 3 of the present invention at different storage times;
FIG. 7a is a UV-vis spectrum of a standard solution composed of pole pieces 7-36 and a series of 5-Cl-PADAB provided in example 3 of the present invention;
FIG. 7b is a graph showing the absorbance-concentration relationship at 566nm for pole pieces 7-36 provided in example 3 of the present invention in a series of 5-Cl-PADAB;
FIG. 8 is a graph of UV-vis spectra of pole pieces 7-9 provided in example 4 of the present invention after 0 days, 1 day, and 9 days of storage.
Detailed Description
The invention is further illustrated by the drawings and the specific examples, which are to be understood as being for the purpose of more detailed description only and are not to be construed as limiting the invention in any way, i.e. not intended to limit the scope of the invention.
The embodiment of the invention provides a color reagent for detecting the dissolution amount of transition metal of a secondary battery electrode material, which is pyridine azo organic matters, and comprises the following components: one or more of 4- (2-Pyridylazo) resorcinol (4- (2-pyridyzo) restorer, PAR), 1- (2-Pyridylazo) -2-naphthol (1- (2-pyridyzo) -2-naphthol, PAN), 4- (5-Chloro-2-pyridine) -azo-1, 3-diaminobenzene (4- (5-Chloro-2-pyridyzo) -1, 3-phenolediamine, 5-Cl-PADAB), 2- (5-Bromo-2-Pyridylazo) -5- (diethylamino) phenol (2- (5-bromo2-pyridyzo) -5- (diethyl-phenolo, 5-Br-PADAP), 1- (2-Thiazolylazo) -2-naphthol (1- (2-thiazolyzo) -2-naphthol, TAN).
The color developing agent can form a complex with transition metal ions in the electrolyte of the secondary battery, is used for testing the absorbance of the complex through ultraviolet-visible spectrophotometry (UV-vis), and is used for obtaining the dissolution amount of the transition metal of the electrode material of the secondary battery through a comparison calibration curve.
The method for detecting the dissolution amount of the transition metal of the electrode material of the secondary battery by using the method is specifically shown in fig. 1, and comprises the following steps:
specifically, the color-developing agent is the pyridine azo organic compound.
The blank electrolyte includes: a solvent and an additive; wherein the solvent specifically comprises: one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and methylethyl carbonate; additives may include those commonly used in lithium batteries and sodium batteries.
the transition metal oxide electrode plate to be measured specifically comprises the following components: an electrode plate of a lithium battery or a sodium battery containing any one of lithium cobaltate, lithium manganate, lithium iron phosphate, ternary material and lithium-rich material; for example, in the case of a lithium battery, the electrolyte to be tested may include a lithium salt, such as: one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bisoxalato borate, lithium difluorooxalato borate and lithium bistrifluoromethane sulfonyl imide.
The transition metal of the secondary battery electrode material specifically comprises transition metal in any one of lithium cobaltate, lithium manganate, lithium iron phosphate, ternary material, lithium-rich material and modified material of the above materials.
The interval of the SOC is 0% -100%. For the electrode plate of the transition metal oxide to be detected in a charged state, adding a surfactant while quantitatively adding an indication electrolyte; the surfactant may include: cetyl trimethylammonium bromide (CTAB), cetyl trimethylammonium chloride (CTAC), cetyl Pyridine Chloride (CPC), cetyl Pyridine Bromide (CPB).
The set concentration of the color developing agent is 50-100 (x 10) -6 mol/L). In the following examples (. Times.10) -6 mol/L) is abbreviated as uM.
And 130, storing the cuvette according to the preset temperature and time, performing ultraviolet-visible spectrophotometry (UV-vis) test on the electrolyte to be tested at a set time node to obtain absorbance, and comparing the absorbance with a calibration curve to obtain the dissolution amount of the transition metal of the electrode material of the secondary battery.
Specifically, the preset temperature is-20 ℃ to 80 ℃. The specific time node can be set according to actual needs, such as 1 day, 2 days, 5 days, and the like.
The calibration curve in the present invention can be obtained as follows: adding a proper amount of salt containing transition metal ions into a certain amount of blank electrolyte, and preparing a series of standard electrolytes containing the transition metal ions with different concentrations; then, each standard solution is subjected to a UV-vis test, and a calibration curve of the transition metal ions in the electrolyte is fitted according to data obtained by the test.
In order to better understand the technical scheme provided by the invention, the following specific applications of the method provided by the embodiment of the invention for detecting the transition metal dissolution amount of the secondary battery electrode material are respectively described in a plurality of specific examples.
Example 1
1. Assembling LiCoO 2 Half cells were charged and discharged 2 times at a rate of 0.05C and then left in a discharged state to obtain a cell having an open circuit voltage of about 3.8V. The battery is disassembled to obtain LiCoO 2 The number of the pole pieces is 3, the numbers are 7-31, 7-39 and 7-53 respectively, the size of the pole pieces is phi 8mm, and the mass of the active substances is 1.807mg, 1.815mg and 2.047mg in sequence.
2. 3mg of PAR was accurately weighed out and dissolved in 9mL of a blank electrolyte (EC: DMC=3:7, vol%) in a glove box to give a solution having a concentration of 1548.87. Mu.M as an indicator electrolyte containing a color developer.
For pole pieces 7-31 and 7-53, the two pole pieces were placed in a cuvette, 26uL of indicator electrolyte was accurately removed using a pipette and added to the cuvette, followed by 377uL of blank electrolyte (EC: dmc=3:7, vol%). The cuvette was sealed. After shaking, one part of the pole piece 7-31 is placed in a constant temperature environment at 45 ℃, and one part of the pole piece 7-53 is placed in a constant temperature environment. For the pole pieces 7-39, the pole pieces were placed in a cuvette, 403uL of blank electrolyte was removed and added thereto, and one of the pole pieces 7-39 was placed in a constant temperature environment at 45 ℃.
3. UV-vis tests were performed after storage for 0, 1, 2, 3, 4 and 8 days, respectively, and the results are shown in FIG. 2. As can be seen from FIG. 2, the sample with the added PAR as a color developer developed a new absorption peak at 571nm after storage for a period of time. Wherein, the test after 0 days indicates that the pole piece is directly tested after being put into the indication electrolyte containing the color reagent. The direction indicated by the arrow in the figure is the direction increasing with time, and the trend of change is different at different wavelengths. The drawings in the following embodiments are the same and will not be described in detail.
A calibration curve is established as follows:
4. 1mg of cobalt (II) acetylacetonate (abbreviated as Co (acac)) was accurately weighed 2 ) In a glove box, the mixture was dissolved in 12mL of the electrolyte to obtain Co (acac) having a concentration of 324.07. Mu.M 2 And (5) a concentrated solution. 6 clean cuvettes were prepared and Co (acac) was added sequentially to the first cuvette 2 Concentrated solution 20uL, indicator electrolyte 84uL, blank electrolyte 1192uL; the other 5 cuvettes were filled with the following three solutions: 20uL, 42uL, 586uL;30uL, 42uL, 576uL;40uL, 42uL, 566uL;60uL, 42uL, 546uL;80uL, 42uL, 526uL; the PAR concentrations in these 6 cuvettes were 100uM and the Co concentrations were 5, 10, 15, 20, 30, 40uM in this order. The 6 cuvettes are placed in a 45 ℃ environment for 24 hours to ensure that the coordination reaction of PAR and Co is fully completed.
5. The liquids in these 6 cuvettes were subjected to UV-vis test and the results are shown in figure 2. FIG. 2 shows that a new absorption peak does appear at 571nm, i.e. it is demonstrated that this peak is the absorption peak of Co-PAR.
6. Considering that the peak of PAR itself may have an influence on the peak at 571nm, a slightly weaker peak at 612nm was chosen as the characteristic peak of Co-PAR, as shown in FIGS. 2 and 3. The absorbance at 612nm was plotted against concentration and a linear fit was made, the results are shown in fig. 4. The absorbance-concentration fitting equation for Co-PAR at 612nm is y=0.01388x+0.00444.
7. The specific amount of Co dissolved in FIG. 2 can be calculated from the scaled curve. The absorbance at 612nm after 8 days of storage of the pole pieces 7-31 is 0.41958, and the concentration of Co obtained by substituting the absorbance into a fitting equation is 30uM. The absorbance of the pole piece 7-53 stored for 8 days at 612nm is 0.12631, and the concentration of Co obtained by substituting the absorbance into a fitting equation is 8.8uM.
The experiment observes that 3 pole pieces store 4 days later in color. The color was seen to be gradually changed to green, indicating that the color change directly observed from the outside was consistent with the calculated concentration change of Co. The conditions of the pole pieces 7-31 and 7-53 are compared, so that the high temperature can promote the quick dissolution of Co and accelerate the failure of the electrode.
Example 2
1. 1mg of PAN was accurately weighed, and dissolved in 3mL of a blank electrolyte in a glove box to obtain a solution having a concentration of 1337.24. Mu.M.
2. The pole pieces 7-40 and 7-42 obtained by the same method as in step 1 of example 1 were placed in a cuvette, 75uL of PAN concentrated solution was accurately removed by using a pipette, and added to the cuvette, and 925uL of blank electrolyte was further added to make the PAN concentration 100uM. The cobalt-containing solutions of 6 concentrations were prepared as in example 1, and characteristic peaks of Co were found at 620nm, with absorbance-concentration fitting equation of y=0.01911x+0.01012. 7-42 were placed in a constant temperature environment at 45℃and 7-40 were subjected to UV-vis tests in a normal temperature environment after storage for 0, 1, 2, 3, 4 and 8 days, respectively, the results are shown in FIG. 5. The absorbance of the pole piece 7-42 at 620nm after 8 days of storage is 0.12879, and the concentration of Co obtained by substituting the absorbance into a fitting equation is 6.2uM, while the concentration of dissolved Co of the pole piece 7-40 is 2.5uM under the same condition. The total liquid in the cuvette of this example was 1mL, so the Co concentration was slightly lower.
Example 3
1. 1mg of 5-Cl-PADAB was accurately weighed and dissolved in 3mL of a blank electrolyte in a glove box to give a 1345.77uM solution.
2. The pole pieces 7-36 obtained in the same manner as in step 1 of example 1 were placed in a cuvette, 37uL of PAN concentrated solution was accurately removed by using a pipette, and added to the cuvette, and 963uL of blank electrolyte was further added to make the 5-Cl-PADAB concentration 50uM. Storing 7-36 at 45 deg.C. UV-vis tests were performed after storage for 0, 1, 2, 3, 4 and 8 days, respectively, and the results are shown in FIG. 6.
3. Since the characteristic peak after the 5-Cl-PADAB and Co are matched is positioned at 566nm, the 5-Cl-PADAB also has an absorption peak at 566 nm. Therefore, 5-Cl-PADAB solutions of 25, 35, 45 and 50uM are prepared firstly, the relation between the absorbance and the concentration of the 5-Cl-PADAB at 566nm is obtained after treatment, and linear fitting is carried out, and the result is shown in figure 7, wherein figure 7a is a UV-vis spectrogram of a standard solution formed by the pole pieces 7-36 provided by the embodiment 3 and a series of 5-Cl-PADAB, and figure 7b is a relation between the absorbance and the concentration of the pole pieces 7-36 provided by the embodiment 3 at 566 nm. The absorbance-concentration fitting equation for 5-Cl-PADAB at 566nm was y=0.00161x+0.00477. A series of standard solutions of different Co concentrations were then prepared as in example 1. The absorbance-concentration fitting equation for Co-5-Cl-PADAB at 566nm was found to be y=0.09319x+0.04373 taking into account the effect of the absorbance of 5-Cl-PADAB at 566 nm.
4. The specific amount of Co dissolved in FIG. 6 can be calculated from the scaled curve. The absorbance at 566nm after 8 days of storage of the pole pieces 7-36 was 0.55468, and the concentration of dissolved Co was calculated to be 4.73uM taking into account the influence of 5-Cl-PADAB.
Example 4
1. Assembling LiCoO 2 Half cells were left in a charged state after a long cycle to give a cell with an open circuit voltage of about 4.6V. The battery is disassembled to obtain LiCoO 2 1 pole pieces, the number is 7-9, the size of the pole pieces is phi 8mm, and the mass of active substances is 1.839mg
2. Using a pipette, accurately remove 65uL of PAR concentrate into a cuvette, then add 935uL of blank electrolyte (EC: DMC=3:7, vol%), accurately weigh 0.364mg CTAB into it to give a PAR concentration of 100uM and a CTAB concentration of 1000uM. The cuvette was sealed. Shaking, and placing the cuvette with the pole pieces 7-9 in a constant temperature environment of 45deg.C
3. UV-vis tests were performed after 0, 1, and 2 days of storage, respectively, and the results are shown in FIG. 8.
According to FIG. 8, co of the pole piece after long circulation is dissolved very fast, a large amount of Co is dissolved in only 1 day, and the dissolution speed is also much faster than that of the pole piece only charged and discharged 2 times. The absorbance at 612nm after 1 day was 0.22136, the Co concentration was 15.6uM in the conversion, and the Co concentration of the pole pieces 7-36 after 8 days of storage was 30uM, considering that the volume of the solution in the cuvette in which the pole pieces 7-9 were placed was twice as much as that in the cuvette in which the pole pieces 7-36 were placed, the dissolution amount after long cycle for only 1 day was higher than that for pole pieces stored for 2 times of cycle for 8 days.
The detection method provided by the invention uses pyridine azo organic matters as a color developing agent for enhancing color development to detect the dissolution amount of transition metal of the secondary battery electrode material, supplements and perfects the defect of directly testing the content of transition metal ions by using a UV-vis method, and can controllably lead the transition metal to form stable complexes so as to realize the detection of the transition metal ions. The method adds the color reagent to enhance the UV-vis signal response of trace transition metal elements in the electrolyte, greatly improves the detection limit, can analyze the failure behavior of the transition metal dissolution in the electrodes in different states under the condition of not damaging the electrode plates, can rapidly judge the failure state of the electrodes by measuring the transition metal dissolution quantity of the electrodes under different conditions (such as different temperatures and different charge and discharge states), and can evaluate the stability of certain electrode materials in the electrolyte to a certain extent. In addition, the method provides possibility for subsequent electrochemical tests, so as to develop in-situ tests. The method provided by the invention has the advantages of high speed, high efficiency and accurate detection.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (6)
1. A method for detecting a dissolved amount of a transition metal of an electrode material of a secondary battery, the method comprising:
adding a proper amount of color developing agent into a certain amount of blank electrolyte to prepare an indication electrolyte containing the color developing agent; the color developing agent is pyridine azo organic matters;
placing a to-be-detected transition metal oxide electrode plate which is subjected to electrochemical charge and discharge to a set state of charge (SOC) in a cuvette, quantitatively adding an indication electrolyte, and adding a blank electrolyte to adjust the concentration of a color developing agent in the solution to the set concentration to obtain the to-be-detected electrolyte;
storing the cuvette according to the preset temperature and time, performing ultraviolet-visible spectrophotometry on the electrolyte to be detected at a set time node to obtain absorbance, and comparing the absorbance with a calibration curve to obtain the dissolution of the transition metal of the secondary battery electrode material;
the color developing agent and transition metal ions in the electrolyte to be detected form a complex, the absorbance of the complex is tested through ultraviolet-visible spectrophotometry, and the dissolution amount of the transition metal of the secondary battery electrode material is obtained through comparison of a calibration curve;
the set concentration of the color developing agent is (50-100) multiplied by 10 -6 mol/L；
The color-developing agent specifically comprises: one or more of 4- (2-Pyridylazo) resorcinol (4- (2-pyridyzo) restorer, PAR), 1- (2-Pyridylazo) -2-naphthol (1- (2-pyridyzo) -2-nap hthol, PAN), 4- (5-Chloro-2-pyridine) -azo-1, 3-diaminobenzene (4- (5-Chloro-2-pyridyzo) -1, 3-phenolediamine, 5-Cl-PADAB), 1- (2-Thiazolylazo) -2-naphthol (1- (2-thiazolyzo) -2-napthol, TAN);
for the transition metal oxide electrode plate to be detected in a charged state, the detection method further comprises the following steps: adding a surfactant while quantitatively adding the indication electrolyte;
the surfactant comprises: cetyl trimethylammonium bromide (CTAB), cetyl trimethylammonium chloride (CTAC), cetyl Pyridine Chloride (CPC), cetyl Pyridine Bromide (CPB).
2. The method of claim 1, wherein the blank electrolyte comprises: solvents and additives;
wherein the solvent specifically comprises: one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate.
3. The detection method according to claim 1, wherein the transition metal oxide electrode sheet to be detected specifically comprises: an electrode plate of a lithium battery or a sodium battery containing any one of lithium cobaltate, lithium manganate, lithium iron phosphate, ternary material and lithium-rich material;
the transition metal of the secondary battery electrode material specifically comprises transition metal in any one of lithium cobaltate, lithium manganate, lithium iron phosphate, ternary material, lithium-rich material and modified material of the above materials.
4. The method according to claim 1, wherein the interval of the SOC is 0% -100%, and the preset temperature is-20 ℃ to 80 ℃.
5. The method of detection according to claim 1, wherein the method further comprises:
adding a proper amount of salt containing transition metal ions into a certain amount of blank electrolyte, and preparing a series of standard electrolytes containing the transition metal ions with different concentrations;
UV-vis testing was performed on each standard solution, and a calibration curve of the transition metal ions in the electrolyte was fitted according to the data obtained from the testing.
6. The method according to claim 5, wherein the salt containing a transition metal ion specifically comprises: one or more of transition metal nitrate, perchlorate, acetylacetonate, hexafluorophosphate, bistrifluoromethylsulfonylimine salts;
the standard electrolyte containing transition metal ions with different concentrations has a concentration of (2-100) x 10 -6 mol/L, the series of different concentrations comprising at least three different concentrations.
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