CN114965344A - Quantitative analysis method for SEI (solid electrolyte interphase) film of lithium ion battery cathode - Google Patents
Quantitative analysis method for SEI (solid electrolyte interphase) film of lithium ion battery cathode Download PDFInfo
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- CN114965344A CN114965344A CN202210527897.8A CN202210527897A CN114965344A CN 114965344 A CN114965344 A CN 114965344A CN 202210527897 A CN202210527897 A CN 202210527897A CN 114965344 A CN114965344 A CN 114965344A
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- pole piece
- powder
- lithium ion
- ion battery
- sei film
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000004445 quantitative analysis Methods 0.000 title claims abstract description 8
- 239000007784 solid electrolyte Substances 0.000 title description 5
- 230000016507 interphase Effects 0.000 title description 4
- 238000000227 grinding Methods 0.000 claims abstract description 17
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 14
- 238000002835 absorbance Methods 0.000 claims abstract description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000010439 graphite Substances 0.000 claims abstract description 6
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 4
- 238000004458 analytical method Methods 0.000 claims description 9
- 238000002329 infrared spectrum Methods 0.000 claims description 7
- 239000011812 mixed powder Substances 0.000 claims description 5
- 239000011149 active material Substances 0.000 claims description 2
- 238000004566 IR spectroscopy Methods 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- -1 for example Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
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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
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
-
- 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
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
- G01N2021/3572—Preparation of samples, e.g. salt matrices
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a quantitative analysis method of a lithium ion battery negative electrode SEI film, which relates to the technical field of lithium ion battery pole piece testing and comprises the following steps: in a glove box, disassembling the formed experimental battery cell to obtain a negative pole piece, and grinding at low temperature to obtain pole piece powder; weighing the pole piece powder and the potassium bromide powder in a glove box, mixing and tabletting, and calculating Li in the infrared spectrogram of the sample 2 CO 3 Absorbance of the characteristic peak; mixing graphite and a lithium carbonate standard substance according to different proportions to obtain a standard mixed sample, mixing and tabletting the standard mixed sample and potassium bromide, and drawing a standard curve according to an infrared spectrogram; subjecting Li in sample spectrogram 2 CO 3 Comparing the absorbance of the characteristic peak with a standard curve so as to obtain Li in the SEI film 2 CO 3 The content of (b) was quantitatively analyzed. The invention utilizes infrared spectroscopy to measure Li in the negative pole piece 2 CO 3 Content, then quantitatively analyzing the growth condition of the SEI film in the battery cell, testing the growth change of the SEI film under different formation conditions, and then exploring a proper conditionThe formation process conditions.
Description
Technical Field
The invention relates to the technical field of lithium ion battery pole piece testing, in particular to a quantitative analysis method of a lithium ion battery negative electrode SEI film.
Background
In the production process of the lithium ion battery, after the battery core is injected with liquid, the step of charging the battery core for the first time is called formation. During the formation of the lithium ion battery, the electrolyte solvent and the lithium salt undergo side reactions, and a solid electrolyte interface film, namely an SEI film, is formed on the negative electrode of the lithium ion battery. The SEI film being Li + Can transmit Li + Carrying out lithium desorption and insertion work; at the same time, is good electronic insulationThe body can effectively prevent the co-embedding of solvent molecules from further damaging the electrode material. However, the formation of SEI film consumes part of Li + And the first charge-discharge irreversible capacity is increased. The increasing SEI film causes capacity fading along with the consumption of electrolyte. Moreover, the SEI film also increases Li + The transmission impedance has an influence on the dynamic performance of the whole system, so that the existence and growth of the SEI film are greatly related to the cycle performance and the service life of the battery cell. The growth of the SEI film is affected by the amount of injected liquid, charging voltage, temperature, and the like, and therefore, it is important to control the thickness of the SEI film by controlling the formation conditions. However, quantitative detection of the SEI film is lacking in the prior art.
The components of the SEI film are greatly affected by the components of the electrolyte, for example, ether electrolytes are prone to produce a lithium-containing alkoxide SEI film, carbonate electrolytes produce a lithium-containing SEI film, and methyl formate electrolytes produce a lithium formate-containing SEI film. At present, most of electrolyte main solvents are carbonate substances, and corresponding battery cell SEI films basically contain Li 2 CO 3 And (3) components.
The infrared spectrometry has the advantages of high detection speed, simple pretreatment, high sensitivity and the like, and belongs to absorption spectra. On the infrared spectrogram of the lithium carbonate standard substance, the sample is 1450cm -1 The left and the right are taken as centers and are at 1400cm -1 And 1500cm -1 A pair of symmetric peaks which are spread out nearby and are [ CO3 ]] 2- Antisymmetric telescopic vibration peak of 870cm -1 Nearby is [ CO3] 2- Out-of-plane bending vibration absorption peaks. Lambert beer law shows that for specific components, the absorbance of the absorption peak and the concentration of the substance are in a linear relation, and if infrared spectroscopy can be adopted for Li in the negative pole piece 2 CO 3 And the quantification is carried out, so that great help is provided for searching for proper formation conditions.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a quantitative analysis method for an SEI (solid electrolyte interphase) film of a negative electrode of a lithium ion battery, which is used for measuring Li in a negative electrode plate by utilizing infrared spectroscopy 2 CO 3 And (4) content, and then quantitatively analyzing the growth condition of the SEI film in the battery cell.
The invention provides a quantitative analysis method of an SEI (solid electrolyte interphase) film of a lithium ion battery cathode, which comprises the following steps of:
s1, carrying out formation on the experimental battery cell of the lithium ion battery;
s2, disassembling the formed experimental battery cell in a glove box to obtain a negative pole piece, and then grinding at low temperature to obtain pole piece powder;
s3, weighing the pole piece powder and the potassium bromide powder in a glove box, mixing and grinding to obtain mixed powder;
s4, tabletting the mixed powder, carrying out infrared spectrum analysis on the powder, and calculating Li in a sample spectrogram 2 CO 3 Absorbance of the characteristic peak;
s5, mixing the graphite and the lithium carbonate standard substance according to different proportions to obtain a standard mixed sample, then mixing the standard mixed sample and potassium bromide for low-temperature grinding, tabletting, carrying out infrared spectrum analysis on the ground sample, and carrying out Li analysis according to a spectrogram 2 CO 3 Drawing a standard curve by the absorbance of the characteristic peak and the content of lithium carbonate in the standard mixed sample;
s6, and mixing Li in the spectrogram of the sample in S4 2 CO 3 Comparing the absorbance of the characteristic peak with a standard curve so as to obtain Li in the negative pole piece 2 CO 3 The content of (b) was quantitatively analyzed.
Preferably, in S2, the active material on the disassembled negative electrode sheet is scraped and then ground at low temperature.
Preferably, cryogrinding is performed using a cryo-grinder; the parameters of the cryo-mill were set as: and circulating for 3 times, precooling for 10min, running time for 2min and rate for 10 CPS.
Preferably, the particle size of the powder for tabletting is larger than or equal to 200 meshes.
In the invention, in the establishment process of the standard curve, Li in a sample spectrogram can be used 2 CO 3 Adjusting the ratio of graphite to lithium carbonate standard substance in the standard sample to ensure Li in the sample 2 CO 3 The content is in the range of standard curve to ensure the accuracy of the analysis result.
Has the advantages that: the invention utilizes redExternal spectrum measurement of Li in negative pole piece 2 CO 3 And (3) content, further quantitatively analyzing the growth condition of the SEI film in the battery cell, and exploring appropriate formation process conditions by testing the growth change of the SEI film under different formation conditions so as to optimize the cycle performance and the service life of the battery.
In the detection process, low-temperature grinding and mixing are adopted, so that the graphite, lithium carbonate and other substances can be fully mixed and uniformly mixed, the local defect of spectral analysis is made up, and the analysis result is more accurate.
Drawings
FIG. 1 is an infrared spectrum of a negative electrode sheet sample in an embodiment of the present invention;
FIG. 2 shows Li in an example of the present invention 2 CO 3 Characteristic peak 1432cm -1 Is plotted against the lithium carbonate content in the standard mixture.
Detailed Description
In the following examples, infrared spectroscopy was performed using a ThermoFisher Nicolet iS50 Fourier transform infrared spectrometer.
The technical solution of the present invention will be described in detail below with reference to specific examples.
Examples
(1) The experimental lithium iron phosphate battery cell is formed at the cut-off voltage of 20 ℃, 0.33C and 3.5V.
(2) And weighing 40 +/-10 mg of the disassembled negative pole piece in a glove box, and putting the negative pole piece into a grinding tank. And setting parameters of a freeze grinding instrument, and placing a sample for grinding.
(3) After the completion of the grinding, the grinding pot was transferred to a glove box, and 3mg of the negative electrode powder and 200mg of the potassium bromide powder after the grinding were collectively placed in a new grinding pot and ground.
(4) Putting the ground mixed powder into a tabletting grinder, tabletting on a tabletting machine, performing infrared spectrum analysis on the powder, wherein the spectrogram is shown in figure 1, and calculating Li in the sample spectrogram 2 CO 3 Absorbance of the characteristic peak;
(5) mixing graphite and lithium carbonate standard substance according to different proportions to obtain standard sample, and thenMixing the standard sample with potassium bromide, grinding at low temperature, tabletting, performing infrared spectrum analysis, and determining Li content in spectrogram 2 CO 3 Characteristic peak 1432cm -1 Drawing a standard curve of the absorbance and the content of lithium carbonate in the standard mixed sample; the standard curve is shown in FIG. 2;
(6) subjecting Li in sample spectrogram 2 CO 3 Comparing the absorbance of the characteristic peak with a standard curve so as to obtain Li in the negative pole piece 2 CO 3 The content of (b) was quantitatively analyzed.
By contrast, Li in the negative electrode plate of the present example 2 CO 3 The content of (D) is 2.13%.
In the invention, the quantitative analysis can be carried out on the SEI film under other formation conditions, such as the SEI film formed under the cut-off voltage of 30 ℃, 0.33C and 3.5V, and the appropriate formation process conditions can be found out by testing the growth change of the SEI film under different formation conditions so as to optimize the cycle performance and the service life of the battery.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (4)
1. A quantitative analysis method of an SEI film of a lithium ion battery cathode is characterized by comprising the following steps:
s1, carrying out formation on the experimental battery cell of the lithium ion battery;
s2, disassembling the formed experimental battery cell in a glove box to obtain a negative pole piece, and then grinding at low temperature to obtain pole piece powder;
s3, weighing the pole piece powder and the potassium bromide powder in a glove box, mixing and grinding to obtain mixed powder;
s4, tabletting the mixed powder, carrying out infrared spectrum analysis on the powder, and calculating Li in a sample spectrogram 2 CO 3 Absorbance of the characteristic peak;
S5、mixing graphite and lithium carbonate standard substance according to different proportions to obtain standard mixed sample, mixing the standard mixed sample with potassium bromide, grinding at low temperature, tabletting, performing infrared spectrum analysis, and analyzing Li in spectrogram 2 CO 3 Drawing a standard curve by the absorbance of the characteristic peak and the content of lithium carbonate in the standard mixed sample;
s6, and mixing Li in the spectrogram of the sample in S4 2 CO 3 Comparing the absorbance of the characteristic peak with a standard curve so as to obtain Li in the negative pole piece 2 CO 3 The content of (b) was quantitatively analyzed.
2. The method for quantitatively detecting the SEI film of the negative electrode of the lithium ion battery as claimed in claim 1, wherein in S2, the active material on the disassembled negative electrode plate is scraped and then ground at low temperature.
3. The method for quantitatively detecting the SEI film of the lithium ion battery cathode is characterized in that a cryogrinding instrument is adopted for low-temperature grinding; the parameters of the cryo-mill were set as: and circulating for 3 times, precooling for 10min, running time for 2min and rate for 10 CPS.
4. The method for quantitatively detecting the SEI film of the lithium ion battery cathode according to claim 1, wherein the granularity of powder for tabletting is not less than 200 meshes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210527897.8A CN114965344A (en) | 2022-05-16 | 2022-05-16 | Quantitative analysis method for SEI (solid electrolyte interphase) film of lithium ion battery cathode |
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| CN202210527897.8A CN114965344A (en) | 2022-05-16 | 2022-05-16 | Quantitative analysis method for SEI (solid electrolyte interphase) film of lithium ion battery cathode |
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| CN114965344A true CN114965344A (en) | 2022-08-30 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116087135A (en) * | 2022-11-17 | 2023-05-09 | 广东广麟材耀新能源材料有限公司 | Evaluation test method and tool for performance of inner glue of aluminum plastic film |
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2022
- 2022-05-16 CN CN202210527897.8A patent/CN114965344A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116087135A (en) * | 2022-11-17 | 2023-05-09 | 广东广麟材耀新能源材料有限公司 | Evaluation test method and tool for performance of inner glue of aluminum plastic film |
| CN116087135B (en) * | 2022-11-17 | 2024-04-26 | 广东广麟材耀新能源材料有限公司 | Evaluation test method for performance of inner layer adhesive of aluminum plastic film |
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