CN103808860B - A kind of lithium ion anode material lithium defect inspection method - Google Patents
A kind of lithium ion anode material lithium defect inspection method Download PDFInfo
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- CN103808860B CN103808860B CN201410060993.1A CN201410060993A CN103808860B CN 103808860 B CN103808860 B CN 103808860B CN 201410060993 A CN201410060993 A CN 201410060993A CN 103808860 B CN103808860 B CN 103808860B
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- iodide
- lithium ion
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 40
- 230000007547 defect Effects 0.000 title claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 28
- 239000010405 anode material Substances 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 8
- 238000007689 inspection Methods 0.000 title abstract 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims abstract description 26
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001514 detection method Methods 0.000 claims abstract description 9
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims abstract description 7
- 229940006461 iodide ion Drugs 0.000 claims abstract description 7
- 238000006138 lithiation reaction Methods 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 28
- 239000010406 cathode material Substances 0.000 claims description 19
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 238000011088 calibration curve Methods 0.000 claims description 8
- -1 iodide ions Chemical class 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910004326 Li(NixCoyMn1-x-y)O2 Inorganic materials 0.000 claims description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 2
- 229910000901 LiFePO4/C Inorganic materials 0.000 claims description 2
- 229910002993 LiMnO2 Inorganic materials 0.000 claims description 2
- 229910003005 LiNiO2 Inorganic materials 0.000 claims description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 2
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 239000011258 core-shell material Substances 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 230000007246 mechanism Effects 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 abstract description 2
- 238000001507 sample dispersion Methods 0.000 abstract 1
- 239000006228 supernatant Substances 0.000 abstract 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of lithium ion anode material lithium defect inspection method, described detection method comprises the following steps: first get lithium ion anode material sample dispersion in acetonitrile solvent, add detection agent lithium iodide and carry out lithiation by control temperature of reaction and time, then reaction solution is washed centrifugal, get supernatant test iodide ion content, obtain the amount of the lithium iodide consumed, finally calculate lithium defect condition and the lithium defect level of described lithium ion anode material.The performance boost of the present invention to lithium ion anode material has important directive function, and detection method is simple and be easy to operation.
Description
Technical Field
The invention relates to a method for detecting lithium defects of a lithium ion cathode material.
Background
Because the lithium ion battery has the advantages of high energy, long service life, high voltage and the like, the lithium ion battery has wide application prospects in various fields such as portable electronic equipment, electric automobiles and the like, and becomes an important direction for the development of new energy industries in China. At present, the mainstream route for synthesizing the lithium ion cathode material is a high-temperature solid-phase method, and due to reasons such as volatilization of a lithium source under a high-temperature condition, a lithium vacancy phenomenon, called as lithium defect, occurs in the cathode material, and the electrochemical performance of the material is finally affected. Therefore, simple and accurate detection and evaluation of lithium defects of the material are of great importance.
Disclosure of Invention
The invention aims to provide a method for detecting lithium defects of a lithium ion cathode material.
In order to solve the technical problems, the invention adopts the technical scheme that: a lithium ion cathode material lithium defect detection method is characterized by comprising the following steps:
(1) drawing an iodide calibration curve by using an iodide standard use solution;
(2) dispersing a lithium ion positive electrode material sample in an acetonitrile solvent to obtain a solution A, wherein the lithium ion positive electrode material is LiFePO4, LiFePO4/C, LiCoO2, LiNiO2, LiMnO2, LiMn2O4, LiMFePO4, LiMCoO2, wherein M is II A, III A, IV A, V A, VI A, III B, V B, VI B, VII B, VIII, and Li (NixCoyMn1-x-y) O2 and Li (NixCoyAl1-x-y) O2, wherein x is less than 1, y is less than 1, and x + y is less than 1, and at least one of compound coating materials of the materials comprises a core-shell structure, a multilayer structure and a mixed structure formed by a plurality of materials; the compound is: al2O3, Al (OH)3, ZrO2, TiO2, SiO2, MgO, ZnO, SnO 2;
(3) adding a detection agent lithium iodide solution into the solution A, wherein the molar ratio of lithium iodide to a lithium ion positive electrode material is as follows: performing reflux lithiation reaction at the temperature of 80 ℃ for 1-10 hours at the ratio of 0.01-2: 1 to obtain a solution B;
(4) centrifuging the solution B at a high speed, ultrasonically washing the solution B by using an organic solvent, and reserving a cleaning solution, wherein the organic solvent is at least one of toluene, benzene, ethanol, methanol, ether, acetone, acetonitrile and chloroform;
(5) and diluting the upper cleaning solution to analyze the iodide ions, obtaining the substance amount of the iodide ions by using an iodide calibration curve, and calculating the consumed iodide ion amount to obtain the lithium defect condition and defect amount of the lithium ion cathode material.
Preferably, the mechanism of the lithiation reaction in step (3) is:
lithium ion cathode material Li1-x+ LiI → Li + LiI of lithium ion anode material3
Preferably, the lithium defect amount and defect rate of the cathode material are calculated by using an iodide calibration curve in the step (1) and an iodide ion analysis method in the step (5), and the formula is as follows:
defect of lithiumN is the amount1-n×n2
Wherein M is the molecular weight of the lithium ion anode material, M is the mass of the lithium ion anode material, n is the dilution multiple of the cleaning solution in the step (5), and n is the molecular weight of the lithium ion anode material1Amount of the substance of lithium iodide described in step (3), n2The amount of the substance of iodide ions obtained in step (5).
The invention has the beneficial effects that:
the method has strong operability, can detect and repair the lithium defects, and is suitable for detecting and correctly evaluating the lithium defects of various lithium ion cathode materials.
Detailed Description
Example 1:
(1) drawing an iodide calibration curve by using an iodide standard use solution;
(2) 0.1580g of LiFePO as an anode material with 1 percent (mol ratio) of theoretical lithium-deficient ions4Dispersing in acetonitrile solvent;
(3) adding a detection agent lithium iodide solution into the solution obtained in the step (2), wherein the molar ratio of lithium iodide to the lithium ion cathode material is as follows: 0.01:1, and carrying out reflux reaction for 1h at the temperature of 80 ℃;
(4) centrifuging the solution in the step (3) at a high speed, ultrasonically washing the solution by using an organic solvent, and reserving a cleaning solution;
(5) diluting the cleaning solution obtained in the step (4) by 100 times for iodide ion analysis, obtaining the substance amount of iodide ions by using an iodide calibration curve, calculating the consumed iodide ion amount to obtain the lithium defect condition and defect amount of the lithium ion cathode material, and adopting the following formulas:
defect amount of lithium ═ n1-n×n2
Wherein M is the molecular weight of the lithium ion anode material, M is the mass of the lithium ion anode material, n is the dilution multiple of the cleaning solution in the step (5), and n is the molecular weight of the lithium ion anode material1Amount of the substance of lithium iodide described in step (3), n2The amount of the substance of iodide ions obtained in step (5).
LiFePO4The synthesis method refers to CN1652999A, and tests show that the lithium defect rate is 1.003 percent and is equivalent to a theoretical value, which shows that the test method has strong operability and can accurately evaluate the lithium defect condition of the lithium ion cathode material.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.
Claims (3)
1. A lithium ion cathode material lithium defect detection method is characterized by comprising the following steps:
(1) drawing an iodide calibration curve by using an iodide standard use solution;
(2) dispersing a lithium ion positive electrode material sample in an acetonitrile solvent to obtain a solution A, wherein the lithium ion positive electrode material is LiFePO4, LiFePO4/C, LiCoO2, LiNiO2, LiMnO2, LiMn2O4, LiMFePO4 and LiMCoO2, wherein M = IIA, IIIA, IVA, VA, VIA, IIIB, VB, VIB, VIIB, VIII and Li (NixCoyMn1-x-y) O2 and Li (NixCoyAl1-x-y) O2, wherein x is less than 1, y is less than 1, and x + y is less than 1', and at least one of the compound coating materials of the materials comprises a core-shell structure, a multilayer structure and a mixed structure formed by a plurality of materials; the compound is: al2O3, Al (OH)3, ZrO2, TiO2, SiO2, MgO, ZnO, SnO 2;
(3) adding a detection agent lithium iodide solution into the solution A, wherein the molar ratio of lithium iodide to a lithium ion positive electrode material is as follows: performing reflux lithiation reaction at the temperature of 80 ℃ for 1-10 hours at the ratio of 0.01-2: 1 to obtain a solution B;
(4) centrifuging the solution B at a high speed, ultrasonically washing the solution B by using an organic solvent, and reserving a cleaning solution, wherein the organic solvent is at least one of toluene, benzene, ethanol, methanol, ether, acetone, acetonitrile and chloroform;
(5) and diluting the upper cleaning solution to analyze the iodide ions, obtaining the substance amount of the iodide ions by using an iodide calibration curve, and calculating the consumed iodide ion amount to obtain the lithium defect condition and defect amount of the lithium ion cathode material.
2. The method for detecting lithium defects in a lithium ion cathode material according to claim 1, wherein: the lithiation reaction mechanism in the step (3) is as follows:
lithium ion cathode material Li1-x+ LiI → Li + LiI of lithium ion anode material3。
3. The method for detecting lithium defects in a lithium ion cathode material according to claim 1, wherein: the lithium defect amount and defect rate of the cathode material are calculated by using the iodide calibration curve in the step (1) and the iodide ion analysis method in the step (5), and the formulas are as follows:
lithium defect amount =
Lithium defect rate (%) =
Wherein,Mthe molecular weight of the lithium ion anode material, m is the mass of the lithium ion anode material, n is the dilution multiple of the cleaning solution in the step (5), and n is the molecular weight of the lithium ion anode material1Amount of the substance of lithium iodide described in step (3), n2The amount of the substance of iodide ions obtained in step (5).
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1461065A (en) * | 2003-06-05 | 2003-12-10 | 福建师范大学 | Preparation of material for modifying lighium vanadium oxide electrode and its application in cell |
| CN102709542A (en) * | 2012-05-25 | 2012-10-03 | 青岛乾运高科新材料股份有限公司 | Method for repairing oxygen defect in preparation process of spinel lithium manganate as lithium-ion cathode material |
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| JPS5713670A (en) * | 1980-06-26 | 1982-01-23 | Japan Storage Battery Co Ltd | Solid electrolyte battery |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1461065A (en) * | 2003-06-05 | 2003-12-10 | 福建师范大学 | Preparation of material for modifying lighium vanadium oxide electrode and its application in cell |
| CN102709542A (en) * | 2012-05-25 | 2012-10-03 | 青岛乾运高科新材料股份有限公司 | Method for repairing oxygen defect in preparation process of spinel lithium manganate as lithium-ion cathode material |
Non-Patent Citations (2)
| Title |
|---|
| Effect of consumption amount of lithium salt on the properties of LiFeP04/C cathode materials;Limei Yang等;《Journal of Alloys and Compounds》;20100212;第496卷;第376-379页 * |
| 锂电池基础科学问题(II)—电池材料缺陷化学;卢侠等;《储能科学与技术》;20130331;第2卷(第2期);第157-163页 * |
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Address after: 230000 Yaohai Industrial Zone, Hefei New District, Anhui, No. D weft Road, No. 7 Patentee after: Gotion High-tech Co., Ltd. Address before: 230000 Yaohai Industrial Park, Anhui, Hefei No. D weft Road, No. 7 Patentee before: Hefei Guoxuan High-Tech Power Energy Co.,Ltd. |