CN102269738A - Method for rapidly determining lithium salt type in lithium ion battery electrolyte - Google Patents
Method for rapidly determining lithium salt type in lithium ion battery electrolyte Download PDFInfo
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- CN102269738A CN102269738A CN2011101131105A CN201110113110A CN102269738A CN 102269738 A CN102269738 A CN 102269738A CN 2011101131105 A CN2011101131105 A CN 2011101131105A CN 201110113110 A CN201110113110 A CN 201110113110A CN 102269738 A CN102269738 A CN 102269738A
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- Prior art keywords
- lithium
- lithium salts
- retention time
- standard
- lithium salt
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- 229910003002 lithium salt Inorganic materials 0.000 title claims abstract description 67
- 159000000002 lithium salts Chemical class 0.000 title claims abstract description 64
- 239000003792 electrolyte Substances 0.000 title claims abstract description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 16
- 230000014759 maintenance of location Effects 0.000 claims abstract description 25
- 238000012360 testing method Methods 0.000 claims abstract description 23
- 239000012086 standard solution Substances 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910013872 LiPF Inorganic materials 0.000 claims abstract description 5
- 101150058243 Lipf gene Proteins 0.000 claims abstract description 5
- 150000002500 ions Chemical class 0.000 claims description 26
- 239000008151 electrolyte solution Substances 0.000 claims description 17
- 238000004587 chromatography analysis Methods 0.000 claims description 15
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 10
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 9
- 238000010790 dilution Methods 0.000 claims description 7
- 239000012895 dilution Substances 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000000039 congener Substances 0.000 claims description 2
- -1 lithium salt anion Chemical class 0.000 abstract description 4
- 229910013188 LiBOB Inorganic materials 0.000 abstract description 3
- 238000004255 ion exchange chromatography Methods 0.000 abstract 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 abstract 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 abstract 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 238000003556 assay Methods 0.000 description 2
- 238000004166 bioassay Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
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Abstract
The invention discloses a method for rapidly determining lithium salt species in lithium ion battery electrolyte, which mainly comprises the step of determining LiPF with the concentration of 5-100mg/L by using ion chromatography6、LiBF4、LiClO4And lithium salt standard solutions such as LiBOB and the like are respectively used for obtaining the standard retention time of various lithium salt anion peaks; and then adding deionized water into an electrolyte sample to be tested to dilute until the concentration of the lithium salt is in a standard concentration range, testing the peak-out retention time of lithium salt anions in the electrolyte sample under the same test condition of the standard solution of the lithium salt by using ion chromatography, and comparing the retention time with the standard retention time to determine the type of the lithium salt in the electrolyte. The electrolyte does not need pretreatment, the testing process is quick and simple, the types of various lithium salts in the electrolyte can be simultaneously determined, and the measuring result is accurate and stable.
Description
Technical field
The present invention relates to the method for lithium salts kind in a kind of fast measuring lithium-ion battery electrolytes, belong to chemical substance authenticate technology field.
Background technology:
Lithium ion battery because have energy density height, output voltage height, have extended cycle life, advantage such as environmental pollution is little, in fields such as electronic product, electric automobile, Aero-Space extremely important application is arranged.Electrode material, electrolytic solution and barrier film are the key components of lithium ion battery, and its performance has directly determined the capacity and the security of battery.Lithium-ion battery electrolytes mainly is made up of solvent and electrolyte lithium salt at present, solvent adopts carbonic ester series high-purity organic solvent more, as vinyl carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC) etc., lithium salts is mainly traditional hexafluoro phosphorus lithium (LiPF
6), tetrafluoro boron lithium (LiBF
4) wait and novel lithium salts di-oxalate lithium borate (LiBOB) and two (trifluoromethane sulfonic acid acyl) imines lithium (LiTFS) etc.Yet, single solvent often can not possess many-sided performance of actual requirement simultaneously on performance, the polycomponent mixed solvent that obtains after multiple solvent mixed by a certain percentage often is better than single solvent, all is the EC base electrolytic solution that contains linear carbonate such as EMC/DEC as present business-like electrolytic solution; Equally, the performance of the mixing lithium salts that obtains after mixing by a certain percentage often is better than single lithium salts, as there are some researches show (J.Power Sources, 2006,159:702-707; Electrochem.Commun., 2006,8:1423-1428), LiBF
4Mix lithium salts with LiBOB (mol ratio 9: 1) and be dissolved in composition electrolytic solution among the PC/EC/EMC (mass ratio 1: 1: 3), be used for LiFePO
4Battery discharges into about 3V with 1C under-50 ℃, can emit 30% of normal temperature capacity, is far superior to contain the electrolytic solution of single lithium salts.Publication number is the patent " quantitative analysis method of lithium-ion battery electrolytes organic component " of CN1712956A, publication number is that the patent " a kind of method of measuring organic component in the lithium-ion electrolyte " of CN1888889A etc. discloses the method for measuring organic component in the lithium-ion battery electrolytes with GC-MS, and publication number is the patent " a kind of ion chromatographic method of measuring lithium salt in the lithium-ion battery electrolytes " of CN1888893A, publication number is that patent " lithium salts assay method in the lithium-ion battery electrolytes " of CN1621808A etc. discloses and uses ion chromatograph, means such as atomic absorption spectrophotometer (AAS) are measured the method for lithium salt in the electrolytic solution.But, the present assay method that does not still have lithium salts kind in the open lithium-ion battery electrolytes of document.
Summary of the invention:
The method that the purpose of this invention is to provide lithium salts kind in a kind of fast measuring lithium-ion battery electrolytes.
The present invention adopts following technical scheme to achieve these goals:
Under certain chromatographic system and operating conditions, every kind of material all has certain retention time, if under identical chromatographic conditions, the retention time of unknown material is identical with standard substance, can think tentatively that then they are same substance,, further in sample, add standard substance in order to improve the reliability of qualitative analysis, if the retention time of measured object is still consistent with standard substance, can think that then they are same substance.The present invention's selection is that the chromatography of ions express-analysis of moving phase is measured in the lithium-ion battery electrolytes with LiPF with the deionized water
6The kind of lithium salts for representative.
The method of lithium salts kind in a kind of fast measuring lithium-ion battery electrolytes is characterized in that may further comprise the steps:
(1) LiPF of preparation 5-100mg/L concentration
6, LiBF
4, LiClO
4Deng three kinds of lithium salts standard solution to be measured,, obtain the standard retention time T that various lithium salts negative ion goes out the peak with chromatography of ions test
1
(2) get the electrolytic solution sample of lithium ion battery, the adding deionized water is diluted to its lithium salt and is in the 5-100mg/L concentration, left standstill aging 5-20 minute, and under the condition identical, went out peak retention time T again with chromatography of ions test lithium salts negative ion wherein with step (1)
2
(3) contrast retention time T
1And T
2, tentatively determine lithium salts kind in the electrolytic solution;
(4) further add congener standard lithium salt solution in the testing sample after dilution is aging, under identical with step (1) the again condition, go out the peak retention time with chromatography of ions test lithium salts negative ion wherein, if the retention time of measured object is still consistent with the standard lithium salts, finally determine lithium salts kind in the electrolytic solution.
Beneficial effect of the present invention:
Electrolytic solution need not pre-service among the present invention, and test process is simple fast, can measure the kind of multiple lithium salts in the electrolytic solution simultaneously, and measurement result is accurately stable.
Description of drawings
Fig. 1 is the LiPF of 5mg/L among the embodiment 1
6, LiBF
4And LiClO
4The chromatography of ions figure of standard solution.
Fig. 2 is a dilution back electrolytic solution sample ions chromatogram to be measured among the embodiment 2.
Embodiment
Embodiment 1:
Accurately take by weighing 0.100g LiPF
6, 0.100g LiBF
4, 0.100g LiClO
4Be dissolved in respectively in the deionized water, constant volume in the 100ml volumetric flask is respectively finished the preparation of the standard solution mother liquor of three kinds of lithium salts then.
Measure a certain amount of lithium salts standard solution mother liquor more respectively, dilution obtains the standard solution of 5-20mg/L, because the present invention is intended to propose to measure the method for lithium salts kind, thereby, this example only selects the standard solution of the 5mg/L lithium salts that settles the standard to go out the retention time at peak in chromatography of ions, Fig. 1 has provided three kinds of lithium salts and gone out the peak situation in chromatography of ions, and as seen, chromatography of ions can be effectively with LiPF
6, LiBF
4And LiClO
4Separate Deng three kinds of lithium salts, thereby realization is by the method for chromatography of ions quick identification lithium salts kind.Under the present embodiment chromatographic condition, LiPF
6, LiBF
4And LiClO
4Go out peak standard retention time and be followed successively by 24.1min, 13.7min and 16.6min Deng three kinds of lithium salts are anionic.
Embodiment 2:
10ml EC/EMC/DEC (1: 1: 1, add the 0.100gLiPF of accurate weighing in electrolyte solvent V/V)
6, 0.100g LiBF
4With 0.100g LiClO
4Deng three kinds of lithium salts, make the lithium-ion battery electrolytes that contains three kinds of lithium salts after fully mixing.Get the above-mentioned electrolytic solution of 5ml, use the deionized water stepwise dilution, after all requiring to leave standstill 10 minutes, each dilution back obtained aqueous solution just begins to dilute next time, up to obtaining the testing sample that every kind of lithium salt content is about 10mg/L, choosing during with embodiment 1 bioassay standard lithium salt solution identical chromatography of ions test condition test the retention time situation that lithium salts negative ion in the testing sample goes out the peak.The A spectral line is that the lithium salts negative ion goes out the peak situation in the testing sample among Fig. 2, exist in the spectrogram retention time be respectively three peaks of 13.4min, 16.5min and 24.1min, with after the retention time at three peaks and the contrast of Fig. 1 standard lithium salts sample retention time, can tentatively determine to contain LiBF in the testing sample
4, LiClO
4And LiPF
6Deng three kinds of lithium salts.In order further to confirm the kind of lithium salts in institute's test sample product, adopt standard addition method in the good testing sample of dilution, to add three kinds of lithium salts standard solution of an amount of 10mg/L, again choosing during with embodiment 1 bioassay standard lithium salt solution identical chromatography of ions test condition test the retention time situation (Fig. 2 B) that lithium salts negative ion in the testing sample goes out the peak, can find obviously that there is tangible enhancing at the peak the when characteristic peak of three kinds of lithium salts under this condition all do not add standard solution, and retention time does not change, thereby can confirm finally that electrolytic solution sample to be measured contains LiBF
4, LiClO
4And LiPF
6Deng three kinds of lithium salts.
Claims (1)
1. the method for lithium salts kind in the fast measuring lithium-ion battery electrolytes is characterized in that may further comprise the steps:
(1) LiPF of preparation 5-100mg/L concentration
6, LiBF
4, LiClO
4Etc. lithium salts standard solution to be measured,, obtain the standard retention time T that various lithium salts negative ion goes out the peak with chromatography of ions test
1
(2) get the electrolytic solution sample of lithium ion battery, the adding deionized water is diluted to its lithium salt and is in the 5-100mg/L concentration, left standstill aging 5-20 minute, and under the condition identical, went out peak retention time T again with chromatography of ions test lithium salts negative ion wherein with step (1)
2
(3) contrast retention time T
1And T
2, tentatively determine lithium salts kind in the electrolytic solution;
(4) further add congener standard lithium salt solution in the testing sample after dilution is aging, under identical with step (1) the again condition, go out the peak retention time with chromatography of ions test lithium salts negative ion wherein, if the retention time of measured object is still consistent with the standard lithium salts, finally determine lithium salts kind in the electrolytic solution.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101131105A CN102269738A (en) | 2011-05-04 | 2011-05-04 | Method for rapidly determining lithium salt type in lithium ion battery electrolyte |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101131105A CN102269738A (en) | 2011-05-04 | 2011-05-04 | Method for rapidly determining lithium salt type in lithium ion battery electrolyte |
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| Publication Number | Publication Date |
|---|---|
| CN102269738A true CN102269738A (en) | 2011-12-07 |
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ID=45052100
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104049067A (en) * | 2014-07-01 | 2014-09-17 | 天津力神电池股份有限公司 | Device and method for determining inorganic salts and additives in lithium battery electrolyte |
| CN105806981A (en) * | 2016-05-04 | 2016-07-27 | 广州天赐高新材料股份有限公司 | Detection method for lithium salt content in lithium-ion battery electrolyte |
| CN106596831A (en) * | 2017-01-23 | 2017-04-26 | 合肥国轩高科动力能源有限公司 | Quantitative detection method for lithium salt remaining on lithium ion battery shell |
| CN107219186A (en) * | 2017-06-06 | 2017-09-29 | 浙江南都电源动力股份有限公司 | The method and device of online quick, batch, accurate detection electrolyte lithium salt |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1888893A (en) * | 2006-07-21 | 2007-01-03 | 天津力神电池股份有限公司 | Ion chromatography method for measuring lithium salt density in lithiumion cell electrolyte |
-
2011
- 2011-05-04 CN CN2011101131105A patent/CN102269738A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1888893A (en) * | 2006-07-21 | 2007-01-03 | 天津力神电池股份有限公司 | Ion chromatography method for measuring lithium salt density in lithiumion cell electrolyte |
Non-Patent Citations (3)
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|---|
| 丁明玉等: "《离子色谱原理与应用》", 31 March 2001 * |
| 于言海等: "离子色谱在锂电池工业的应用", 《第13届离子色谱学术报告会论文集》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104049067A (en) * | 2014-07-01 | 2014-09-17 | 天津力神电池股份有限公司 | Device and method for determining inorganic salts and additives in lithium battery electrolyte |
| CN105806981A (en) * | 2016-05-04 | 2016-07-27 | 广州天赐高新材料股份有限公司 | Detection method for lithium salt content in lithium-ion battery electrolyte |
| CN106596831A (en) * | 2017-01-23 | 2017-04-26 | 合肥国轩高科动力能源有限公司 | Quantitative detection method for lithium salt remaining on lithium ion battery shell |
| CN107219186A (en) * | 2017-06-06 | 2017-09-29 | 浙江南都电源动力股份有限公司 | The method and device of online quick, batch, accurate detection electrolyte lithium salt |
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Application publication date: 20111207 |