CN109738823B - Method for testing and evaluating performance of electrolyte system of silicon-based negative electrode half cell - Google Patents
Method for testing and evaluating performance of electrolyte system of silicon-based negative electrode half cell Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 99
- 239000010703 silicon Substances 0.000 title claims abstract description 99
- 239000003792 electrolyte Substances 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000012360 testing method Methods 0.000 title claims abstract description 22
- 239000002086 nanomaterial Substances 0.000 claims abstract description 65
- 238000004458 analytical method Methods 0.000 claims abstract description 43
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 40
- 239000000126 substance Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims description 24
- 159000000002 lithium salts Chemical class 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 23
- 239000005486 organic electrolyte Substances 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 11
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003575 carbonaceous material Substances 0.000 claims description 6
- 239000002608 ionic liquid Substances 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000004065 semiconductor Substances 0.000 claims description 6
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 6
- 238000002076 thermal analysis method Methods 0.000 claims description 6
- 230000000930 thermomechanical effect Effects 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 239000011856 silicon-based particle Substances 0.000 claims description 5
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 4
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 3
- 238000004630 atomic force microscopy Methods 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 3
- 150000004292 cyclic ethers Chemical class 0.000 claims description 3
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 3
- 238000004455 differential thermal analysis Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 150000002632 lipids Chemical class 0.000 claims description 3
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000007769 metal material Substances 0.000 claims description 3
- 239000002070 nanowire Substances 0.000 claims description 3
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 3
- 239000000523 sample Substances 0.000 claims description 3
- 239000002620 silicon nanotube Substances 0.000 claims description 3
- 229910021430 silicon nanotube Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
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- 238000002411 thermogravimetry Methods 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical class OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 claims description 2
- 239000005543 nano-size silicon particle Substances 0.000 claims description 2
- 238000000921 elemental analysis Methods 0.000 claims 1
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- 239000002210 silicon-based material Substances 0.000 description 15
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 8
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- PGRMNXHYAZYNPG-UHFFFAOYSA-N fluoro hydrogen carbonate Chemical class OC(=O)OF PGRMNXHYAZYNPG-UHFFFAOYSA-N 0.000 description 1
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Abstract
本申请公开了一种用于测试和评价硅基负极半电池的电解液体系性能的方法，包括：利用硅的化学组分单一、形貌单一的微纳米结构制成的微纳米结构模板形式的硅基负极和待评估的电解液制成硅基负极半电池，利用金属作为对电极，制成正极半电池；在设定的温度和设定的电池性能测试程序下运行所制成的硅基负极半电池，进行电池性能测试；从运行后的所述硅基负极半电池中取出微纳米结构模板，并对所述微纳米结构模板进行清洁处理；对经清洁处理后的所述微纳米结构模板进行设定的分析。利用本申请的方法可以实现系统且细致地研究不同电解液体系情形中硅表面固体电解质层膜的性能。
The present application discloses a method for testing and evaluating the performance of an electrolyte system of a silicon-based negative electrode half-cell, comprising: using a micro-nano structure template made of silicon with a single chemical composition and a single morphology in the form of a micro-nano structure template. The silicon-based negative electrode and the electrolyte to be evaluated are made into a silicon-based negative electrode half-cell, and the metal is used as the counter electrode to make a positive-electrode half-cell; the fabricated silicon-based half-cell is run under the set temperature and the set battery performance test procedure. Negative half-cell, battery performance test; take out the micro-nano structure template from the silicon-based negative half-cell after operation, and clean the micro-nano structure template; The template performs the set analysis. Using the method of the present application, it is possible to systematically and meticulously study the performance of the solid electrolyte layer film on the silicon surface in the case of different electrolyte systems.
Description
Technical Field
The present application relates to the field of lithium ion batteries, and more particularly, to a method for testing and evaluating the performance of an electrolyte system of a silicon-based negative half-cell.
Background
With the rapid development of economy, the global energy situation is becoming more and more severe, the demand of traditional primary energy sources such as coal and oil is still continuously increasing, and meanwhile, the damage to the global ecological environment is also aggravated. Therefore, the development and application of clean, low-carbon, environment-friendly and renewable energy sources have become the subject of urgent need for co-exploration. With the development of energy storage technology, the application of renewable energy sources such as wind energy, solar energy and the like is greatly improved. Currently, relatively hot energy storage lithium ion batteries are widely used in portable electronic devices such as notebooks and smart phones. However, in order to realize the application of the lithium ion battery to the new energy automobile with clean environmental protection and no pollution discharge, the development of a new generation of lithium ion battery with high energy, high power density and high safety performance is urgent.
Due to the high lithium storage capacity (the theoretical capacity is 4200mAh/g) and abundant resources, the silicon material is considered to be one of ideal candidate materials for developing a new generation of high specific energy and high power density lithium ion battery negative electrode material. However, the silicon material has a fast capacity decay during use, so that the practical application thereof is limited. Analysis shows that the silicon material has larger lithium-intercalated volume expansion and contraction, so that the whole structure of the material is damaged, the conductivity of the material is reduced, and the main reason for the faster capacity attenuation of the material is. Therefore, the inhibition of the volume expansion of the silicon material and the improvement of the structural stability and the conductivity of the material have great significance for improving the cycle stability of the silicon material.
As a negative electrode material for lithium batteries, like commercial graphite materials, electrolyte is decomposed on the surface thereof during charge and discharge cycles to form a solid electrolyte layer (SEI) that is adsorbed on the silicon surface. The composition, morphology, distribution and the like of the solid electrolyte layer can greatly influence the performance of the battery, including cycle performance, rate performance, high and low temperature performance and the like, and especially has important significance for stabilizing the structural stability of the silicon material and ensuring the cycle stability. Therefore, different electrolyte systems are developed to represent the performance of the solid electrolyte layer film on the silicon surface, and the method has important significance for improving the performance of the silicon-based material electrode.
However, the silicon-based materials commercialized at present are mostly made of nano silicon powder and mixed with various materials, so that it is difficult to systematically and finely study the performance of a solid electrolyte layer (SEI) film on the silicon surface under different electrolyte systems.
Therefore, a method specially used for testing, evaluating and researching the performance of the electrolyte system of the silicon-based negative electrode half cell is urgently needed.
Disclosure of Invention
The present application is proposed to solve the above-mentioned technical problems. Embodiments of the present application provide a method for testing and evaluating the performance of an electrolyte system of a silicon-based negative electrode battery, which can systematically and carefully study the performance of a solid electrolyte layer film on a silicon surface in different electrolyte system situations.
Embodiments of the present application provide a method for testing and evaluating the performance of an electrolyte system of a silicon-based negative half-cell, comprising:
a half-cell preparation step, namely preparing a silicon-based negative half-cell by utilizing a silicon-based negative electrode in the form of a micro-nano structure template and electrolyte to be evaluated, and preparing a positive half-cell by utilizing metal as a counter electrode, wherein the micro-nano structure template is prepared by using a micro-nano structure with single chemical component and single appearance, and preferably, the metal is lithium;
a battery performance testing step, namely running the manufactured silicon-based negative electrode half battery under a set temperature and a set battery performance testing program to test the battery performance;
a micro-nano structure template cleaning step, namely taking out the micro-nano structure template from the operated silicon-based negative electrode half cell, and cleaning the micro-nano structure template;
and a micro-nano structure template analysis step, namely performing set analysis on the micro-nano structure template after cleaning treatment.
In one embodiment, when the micro-nano structure template is manufactured, the micro-nano structure with a single chemical component and a single appearance of silicon is subjected to surface modification.
In one embodiment, the micro-nano structure with a single chemical component and a single shape of silicon has a shape of a rod, a hemisphere, a cone, a column or an ellipse.
In one embodiment, the size of the micro-nano structure monomer with a single chemical component and a single shape of silicon is 10nm-10um, preferably 10nm-1um, and more preferably 10nm-500 nm.
In one embodiment, the surface modification comprises surface coating of one or more of carbon material, metal oxide material, semiconductor material and solid electrolyte material,
wherein the carbon material is amorphous carbon or graphene carbon;
wherein the metal material is one or a mixture of gold, silver, copper and iron;
wherein, the metal oxide is one or a combination of more of aluminum oxide, titanium oxide, niobium oxide, zirconium oxide and magnesium oxide;
wherein the semiconductor material comprises zinc oxide and/or gallium arsenide;
wherein the solid electrolyte material is a garnet-type solid electrolyte and/or a NASCION-type solid electrolyte.
In one embodiment, the silicon-based negative electrode is a negative electrode active material containing silicon, and comprises one or more combinations of a three-dimensional silicon structure, a two-dimensional silicon film, a one-dimensional silicon nanowire, a silicon nanotube, a micron silicon particle, a nanometer silicon particle and a silicon monoxide, and a derivative thereof subjected to post-processing.
In one embodiment, the electrolyte to be evaluated includes one or more of an ionic liquid, a lipid organic liquid, a carbonate, an ether organic electrolyte, a sulfone or sulfoxide organic electrolyte, a nitrile organic electrolyte, a silicon-based electrolyte, a phosphorus-based electrolyte and derivatives thereof, and preferably, the electrolyte is one or more of a linear carbonate organic electrolyte, a cyclic carbonate organic electrolyte, a linear ether electrolyte and a cyclic ether electrolyte and derivatives thereof.
In a further embodiment, the electrolyte to be evaluated further comprises a lithium salt and an additive, wherein the lithium salt is a phosphorus element-containing lithium salt, a boron element-containing lithium salt, a nitrogen element-containing lithium salt or an inorganic lithium salt, and preferably, the lithium salt is one or a mixture of several of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium dioxalate borate, lithium bistrifluoromethanesulfonylimide, lithium bifluorosulfonylimide and derivatives thereof.
In a further embodiment, the electrolyte to be evaluated further comprises an additive, wherein the additive is one or more of fluoro carbonates, unsaturated organic electrolyte, silicon-based polymer, lithium salt, sodium salt, potassium salt, ionic liquid and derivatives thereof.
In one embodiment, in the micro-nano structure template cleaning step, the micro-nano structure template is cleaned and dried by using an organic solvent, wherein the organic solvent is a volatile linear carbonate organic solvent, preferably, the organic solvent is dimethyl carbonate or diethyl carbonate.
In one embodiment, in the micro-nano structure template analysis step, the setting analysis is one or a combination of more of morphology analysis, element analysis, thermal analysis and mechanical analysis of the micro-nano structure template,
wherein, the appearance analysis is one or a combination of a plurality of scanning electron microscope analysis, a transmission electron microscope, an optical microscope and a scanning probe microscope;
wherein, the element analysis is one or a combination of more of an atomic emission spectrometer and an energy dispersion X-ray spectrometer;
wherein, the thermal analysis is one or a combination of more of differential thermal analysis, thermogravimetric analysis, differential scanning calorimetry analysis, static thermomechanical analysis and dynamic thermomechanical analysis;
wherein the mechanical analysis is atomic force microscopy analysis.
Compared with the prior art, the method for testing and evaluating the performance of the electrolyte system of the silicon-based negative electrode half cell according to the embodiment of the application can represent the performance of the solid electrolyte layer films on the silicon surface of different electrolyte systems, and systematically and finely research the performance of the solid electrolyte layer films on the silicon surface under different electrolyte systems.
Drawings
The above and other objects, features and advantages of the present application will become more apparent by describing in more detail embodiments of the present application with reference to the attached drawings. The accompanying drawings are included to provide a further understanding of the embodiments of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the principles of the application. In the drawings, like reference numbers generally represent like parts or steps.
Fig. 1 shows a flow diagram of a method for testing and evaluating the performance of an electrolyte system of a silicon-based anode half-cell according to an embodiment of the present application.
Fig. 2 shows a schematic diagram of nano-pillar silicon with a single chemical composition and a single morphology.
Fig. 3 shows an SEM image after three weeks of charging and discharging according to example 1 of the present application.
Fig. 4 shows an SEM image after three weeks of charge and discharge according to example 2 of the present application.
Fig. 5 shows an SEM image after three weeks of charge and discharge according to example 3 of the present application.
Fig. 6 shows an SEM image after three weeks of charge and discharge according to example 4 of the present application.
Fig. 7 shows an SEM image after three weeks charge and discharge according to example 5 of the present application.
Fig. 8 shows an xps C1 s plot after three weeks charge and discharge according to example 1 of the present application.
Fig. 9 shows an xps C1 s plot after three weeks charge and discharge according to example 2 of the present application.
Fig. 10 shows an xps C1 s plot after three weeks charge and discharge according to example 3 of the present application.
Fig. 11 shows an xps C1 s plot after three weeks charge and discharge according to example 4 of the present application.
Fig. 12 shows an xps C1 s plot after three weeks charge and discharge according to example 5 of the present application.
Fig. 13 shows a first-cycle charge-discharge curve according to example 1 of the present application.
Fig. 14 shows a first-cycle charge-discharge curve according to example 2 of the present application.
Fig. 15 shows first cycle charge and discharge curves according to example 3 of the present application
Fig. 16 shows a first-cycle charge-discharge curve according to example 4 of the present application.
Fig. 17 shows a first-cycle charge-discharge curve according to example 5 of the present application.
Detailed Description
Hereinafter, example embodiments according to the present application will be described in detail with reference to the accompanying drawings. It should be understood that the described embodiments are only some embodiments of the present application and not all embodiments of the present application, and that the present application is not limited by the example embodiments described herein.
Summary of the application
As described above, the composition, morphology, distribution, etc. of the solid electrolyte layer greatly affect the performance of the battery, and especially have important significance in stabilizing the structural stability of the silicon material and ensuring the cycling stability. Different electrolyte systems form different solid electrolyte layer films on the silicon surface, so the systematic and careful study on the performance of the solid electrolyte layer films on the silicon surface in different electrolyte systems is a problem to be solved.
In order to solve the technical problem, the basic concept of the application is to provide a method for testing and evaluating the performance of an electrolyte system of a silicon-based negative electrode half-cell based on a micro-nano structure with single chemical component and single appearance and a structure obtained by modifying the surface of the micro-nano structure, wherein the method is based on the fact that the performance of a solid electrolyte layer film on the surface of silicon in different electrolyte system situations can be systematically and carefully researched.
It should be noted that the above basic concept of the present application can be applied not only to the electrolyte system of the silicon-based negative electrode half cell, but also to other objects, such as a non-silicon-based negative electrode half cell, or the electrolyte system of a silicon-based negative electrode cell, a non-silicon-based negative electrode cell, and the like.
In addition, it should be noted that although the silicon column micro-nano structure with a single chemical component and a single morphology is used in the present application to facilitate the study of the morphology change and the chemical component after the cycle, the micro-nano structure containing multiple chemical components, multiple silicon column micro-nano structures with regular or irregular morphologies, or other materials may also be used.
Having described the general principles of the present application, various non-limiting embodiments of the present application will now be described with reference to the accompanying drawings.
Examples of the inventionSexual method
Fig. 1 illustrates a flow chart of a method for testing and evaluating electrolyte system performance of a silicon-based anode half-cell according to an embodiment of the present application.
As shown in fig. 1, the method for testing and evaluating the performance of the electrolyte system of the silicon-based negative electrode half cell includes a half cell preparation step, a cell performance testing step, a micro-nano structure template cleaning step, and a micro-nano structure template analysis step.
Hereinafter, each step will be described in detail.
In the preparation step of the half-cell, a silicon-based negative electrode in the form of a micro-nano structure template and electrolyte to be evaluated are utilized to prepare a silicon-based negative electrode half-cell, metal is used as a counter electrode to prepare a positive electrode half-cell, wherein the micro-nano structure template is prepared on the basis of a micro-nano structure with single chemical component and single appearance and a structure obtained by modifying the surface of the micro-nano structure, and the metal counter electrode is selected from lithium.
In one embodiment, the shape of the micro-nano structure with a single chemical component and a single shape can be a rod, a hemisphere, a cone, a column or an ellipse. The micro-nano structure shown in fig. 2 is nano columnar silicon with single chemical component and single appearance. By adopting the embodiment, the micro-nano structure is simple in appearance and easy to manufacture.
In one embodiment, the size of the monomer of the micro-nano structure with single chemical component and single appearance is 10nm-10um, the optimized size is 10nm-1um, and the optimal size is 10nm-500 nm.
In one embodiment, the surface modification of the micro-nano structure comprises a surface coating carbon material, a metal oxide material, a semiconductor material and a solid electrolyte material. Wherein the carbon material is amorphous carbon and/or graphene carbon; the metal material is one or a mixture of gold, silver, copper and iron; the metal oxide is one or a combination of more of aluminum oxide, titanium oxide, niobium oxide, zirconium oxide and magnesium oxide; the semiconductor material comprises zinc oxide and/or gallium arsenide; the solid electrolyte material is garnet-type solid electrolyte and/or NASCION-type solid electrolyte. In the embodiment, the surface of the micro-nano structure is coated with other materials, so that the reaction between silicon and electrolyte can be reduced, the lithium release of the silicon material is inhibited, the volume expansion of the silicon material is further inhibited, and the structural stability of the silicon material is improved.
In one embodiment, the silicon-based negative electrode is a negative electrode active material containing silicon, and comprises one or more combinations of a three-dimensional silicon structure, a two-dimensional silicon film, a one-dimensional silicon nanowire, a silicon nanotube, a micron silicon particle, a nanometer silicon particle and a silicon monoxide, and a derivative thereof subjected to post-processing. In this embodiment, the silicon-containing negative electrode active material is used to manufacture the micro-nano structure template, so that lithium can be prevented from being released from the silicon material, the volume expansion of the silicon material can be further prevented, and the structural stability of the silicon material can be improved.
In one embodiment, the silicon-based negative electrode electrolyte system comprises a lithium salt, an electrolyte and an additive, wherein the lithium salt is a phosphorus element-containing lithium salt, a boron element-containing lithium salt, a nitrogen element-containing lithium salt or an inorganic lithium salt, preferably, the lithium salt is one or a mixture of several of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium dioxalate borate, lithium bistrifluoromethanesulfonylimide, lithium bifluorosulfonylimide and derivatives thereof; the electrolyte is one or a mixture of more of ionic liquid, lipid organic liquid, carbonates, ether organic electrolyte, sulfones or sulfoxides organic electrolyte, nitrile organic electrolyte, silicon-based electrolyte and phosphorus-based electrolyte and derivatives thereof, and preferably, the electrolyte is one or a mixture of more of linear carbonate organic electrolyte, cyclic carbonate organic electrolyte and linear ether electrolyte and cyclic ether electrolyte and derivatives thereof; the additive is one or more of fluoro-carbonates, unsaturated organic electrolyte, silicon-based polymer, lithium salt, sodium salt, potassium salt and ionic liquid and derivatives thereof. By adopting the electrolyte system of the embodiment, the performance of the solid electrolyte layer film on the silicon surface under the electrolyte system and the influence of the electrolyte system on the performance of the solid electrolyte layer film on the silicon surface can be systematically and finely studied.
In the step of testing the battery performance, the manufactured silicon-based negative electrode half battery is operated under the set temperature and the set battery performance test program to test the battery performance.
In one embodiment, the set temperature is room temperature. In this embodiment, since the set temperature is room temperature, no cooling or heating equipment is required, so that the method according to the present application is convenient to operate and the required equipment structure is more simplified.
In one embodiment, the set battery test procedure was to discharge to 300uAh at a constant current of 30uA, rest for 30s, then charge to 300uA to 2V at a constant current, and cycle for 3 weeks. By adopting the embodiment, the performance of the solid electrolyte layer film on the silicon surface under the electrolyte system and the influence of the electrolyte system on the performance of the solid electrolyte layer film on the silicon surface can be more accurately researched through the circulation mode and the multiple circulation.
In the micro-nano structure template cleaning step, in an embodiment, the cleaning process is to clean and dry the micro-nano structure template by using an organic solvent, preferably, the organic solvent is a volatile linear carbonate organic solvent, and more preferably, the organic solvent is dimethyl carbonate or diethyl carbonate. In this embodiment, adopt organic solvent, wash, can reduce the harm of washing solvent to micro-nano structure template, especially, adopt volatile organic solvent, can also reduce the residue of organic solvent on micro-nano structure template, further reduce the harm of washing solvent to micro-nano structure template.
In the micro-nano structure template analysis step, the setting analysis is one or a combination of more of appearance analysis, element analysis, thermal analysis and mechanical analysis of the micro-nano structure template, wherein the appearance analysis is one or a combination of more of scanning electron microscope analysis, transmission electron microscope, optical microscope and scanning probe microscope; wherein, the element analysis is one or a combination of more of an atomic emission spectrometer and an energy dispersion X-ray spectrometer; wherein, the thermal analysis is one or a combination of more of differential thermal analysis, thermogravimetric analysis, differential scanning calorimetry analysis, static thermomechanical analysis and dynamic thermomechanical analysis; wherein the mechanical analysis is atomic force microscopy analysis. By adopting the embodiment, the performance of the silicon surface solid electrolyte layer film under the electrolyte system and the influence of the performance on the silicon surface solid electrolyte layer film can be systematically and carefully researched.
Examples of the invention
Several examples of applications of the method according to the present application for testing and evaluating the performance of electrolyte systems of silicon-based anode half-cells are listed below, wherein the same silicon-based anode is made into a silicon-based anode half-cell with different electrolytes, or the same silicon-based anode is placed in different electrolyte systems.
Example 1: the silicon-based negative electrode adopts a micron conical silicon structure, the diameter of the silicon-based negative electrode is 3um, and the height of the silicon-based negative electrode is 10 um. The electrolyte system is selected to be a mixed solution of 1M LiPF6 dissolved in Ethylene Carbonate (EC) and dimethyl carbonate (DMC), wherein EC/DMC is 1: 1. The micro-pyramidal silicon structure forms a first half-cell with an electrolyte system and the metallic lithium acts as a counter electrode, forming a second half-cell. After the first half cell and the second half cell were allowed to stand together for 6 hours, a cell performance test was performed. The battery test procedure was to discharge at a constant current of 25uA to 25uAh, rest for 30s, then charge at a constant current of 25uA to 2V, and cycle for 50 weeks. After cycling, the cells were disassembled, after repeated rinsing with DMC in a glove box, the nano-cone silicon was formed, left to stand for 24 hours, air dried, and tested using a vacuum transfer box for electron scanning microscopy (SEM) and X-ray photoelectron spectroscopy (XPS).
Example 2 differs from example 1 only in that the electrolyte system was chosen to be 1M LiPF6 soluble in (EC/DMC 1:2) + FEC + 2% VC and will not be described again.
Example 3 differs from example 1 only in that the electrolyte system was chosen to be 1M LiPF6 soluble (EC \ PC \ DMC) and the additive VC was added and will not be described here.
Example 4 differs from example 1 only in that the electrolyte system was chosen to be 1M LiBF4 soluble (EC/DMC) and will not be described in detail here.
Example 5 differs from example 1 only in that the electrolyte system was chosen to be 1M lidob soluble (EC/DMC) and will not be described here.
Fig. 3 to 7 show SEM images of examples 1 to 5 after three weeks of charge and discharge, respectively. As shown in fig. 3 to 7, the SEM images of examples 1 to 5 after three-week cycling were clearly different. In example 1, after the silicon surface solid electrolyte layer film is formed, a significant crack exists, and during the next week of charge and discharge, the exposed Si can continue to react with the electrolyte to continuously form a silicon surface solid electrolyte layer film, so that the coulombic efficiency of the silicon surface solid electrolyte layer film is very low; in example 2, the silicon surface solid electrolyte layer film is very uniform and regular, and a dense silicon surface solid electrolyte layer film has been formed in the second week, so coulombic efficiency is high, and cycle performance is also improved; examples 3 and 4 are also obviously improved compared with example 1; the silicon surface solid electrolyte layer of example 5 was more densely covered with a film with only a slight crack, but was superior to examples 3 and 4. As is apparent from the results of the SEM images, the relationship between the performance or coulombic efficiency of the silicon surface solid electrolyte layer film in each example is: example 2> example 5> example 4> example 3> example 1.
Fig. 8 to 12 show schematic diagrams of xps C1 s after three-week charge and discharge of examples 1 to 5. Analysis of the chemical composition of the samples after cycling was performed and fig. 8 to 12 show xps C1 s peaks, the composition of most of these five examples being C-C/C-H, C-O, O-C-O, CO32-, but the intensities between the examples were very different. Comparison of example 1 with example 2 clearly shows the presence of CO 32-in example 1, mainly Li2CO3Due to the reaction of Li with EC to form Li2CO3And CH4(ii) a The addition of FEC and VC in example 2 would cause Li to react preferentially with FEC to form LiF, hindering the reaction of Li with EC. In example 4, C — H and C ═ O were stronger on the surface of the electrolyte containing boron, mainly because the lithium salt containing boron reacted preferentially with Li, hindering the reaction between Li and EC.
Fig. 13 to 17 show first-cycle charge and discharge curves according to examples 1 to 5 of the present application. As shown, the first cycle efficiency of example 1 is 53%, the first cycle efficiency of example 2 is 83%, the first cycle efficiency of example 3 is 67%, the first cycle efficiency of example 4 is 68%, and the first cycle efficiency of example 5 is 75%. It is clear from fig. 13 to 17 that the first cycle efficiency of example 2 is the best, followed by example 5, and example 4 is almost the same as example 3, and the worst is example 1 without addition, and then the relationship between the properties of the silicon surface solid electrolyte layer film in each example can be obtained from fig. 13 to 17 as well: example 2> example 5> example 4> example 3> example 1.
As can be seen from fig. 3 to 17, the different electrolyte systems used in examples 1 to 5 have a significant effect on the performance of the silicon surface solid electrolyte layer films using the method for testing and evaluating the performance of the electrolyte system of a silicon-based negative half cell according to the present application.
The foregoing describes the general principles of the present application in conjunction with specific embodiments, however, it is noted that the advantages, effects, etc. mentioned in the present application are merely examples and are not limiting, and they should not be considered essential to the various embodiments of the present application. Furthermore, the foregoing disclosure of specific details is for the purpose of illustration and description and is not intended to be limiting, since the foregoing disclosure is not intended to be exhaustive or to limit the disclosure to the precise details disclosed.
The block diagrams of devices, apparatuses, systems referred to in this application are only given as illustrative examples and are not intended to require or imply that the connections, arrangements, configurations, etc. must be made in the manner shown in the block diagrams. These devices, apparatuses, devices, systems may be connected, arranged, configured in any manner, as will be appreciated by those skilled in the art. Words such as "including," "comprising," "having," and the like are open-ended words that mean "including, but not limited to," and are used interchangeably therewith. The words "or" and "as used herein mean, and are used interchangeably with, the word" and/or, "unless the context clearly dictates otherwise. The word "such as" is used herein to mean, and is used interchangeably with, the phrase "such as but not limited to".
It should also be noted that in the devices, apparatuses, and methods of the present application, the components or steps may be decomposed and/or recombined. These decompositions and/or recombinations are to be considered as equivalents of the present application.
The previous description of the disclosed aspects is provided to enable any person skilled in the art to make or use the present application. Various modifications to these aspects will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other aspects without departing from the scope of the application. Thus, the present application is not intended to be limited to the aspects shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
The foregoing description has been presented for purposes of illustration and description. Furthermore, the description is not intended to limit embodiments of the application to the form disclosed herein. While a number of example aspects and embodiments have been discussed above, those of skill in the art will recognize certain variations, modifications, alterations, additions and sub-combinations thereof.
Claims (17)
1. A method for testing and evaluating the performance of an electrolyte system of a silicon-based negative half-cell, comprising:
preparing a half-cell, namely preparing a silicon-based negative half-cell by using a silicon-based negative electrode in a micro-nano structure template form and electrolyte to be evaluated, and preparing a positive half-cell by using metal as a counter electrode;
a battery performance testing step, namely running the manufactured silicon-based negative electrode half battery under a set temperature and a set battery performance testing program to test the battery performance;
a micro-nano structure template cleaning step, namely taking out the micro-nano structure template from the operated silicon-based negative electrode half cell, and cleaning the micro-nano structure template;
a micro-nano structure template analysis step of performing set analysis on the micro-nano structure template after cleaning treatment,
the micro-nano structure template is made of a micro-nano structure which is single in chemical components, single in appearance and regularly arranged, so that appearance change and chemical component change of the micro-nano structure template after circulation of the micro-nano structure template under different electrolyte systems can be conveniently researched, and therefore the influence of the electrolyte systems on the performance of the solid electrolyte layer film on the silicon surface can be tested and evaluated.
2. The method of claim 1, wherein the micro-nano structure template is prepared by performing surface modification on a silicon micro-nano structure with a single chemical component, a single shape and a regular arrangement.
3. The method of claim 2, wherein the micro-nano structure with a single chemical composition and a single shape has a rod shape, a semi-sphere shape, a cone shape, a column shape or an ellipse shape.
4. The method of claim 1, wherein the silicon has a single chemical composition, a single morphology, and a monomer size of regularly arranged micro-nano structures of 10nm to 10 um.
5. The method of claim 2, wherein the surface modification comprises surface coating with one or more of carbon material, metal oxide material, semiconductor material, and solid electrolyte material,
wherein the carbon material is amorphous carbon or graphene carbon;
wherein the metal material is one or a mixture of gold, silver, copper and iron;
wherein, the metal oxide is one or a combination of more of aluminum oxide, titanium oxide, niobium oxide, zirconium oxide and magnesium oxide;
wherein the semiconductor material comprises zinc oxide and/or gallium arsenide;
wherein the solid electrolyte material is a garnet-type solid electrolyte and/or a NASCION-type solid electrolyte.
6. The method according to claim 1, wherein the silicon-based negative electrode is a negative active material containing silicon, and comprises one or more of a three-dimensional silicon structure, a two-dimensional silicon thin film, a one-dimensional silicon nanowire, a silicon nanotube, a micron silicon particle, a nano silicon particle, and a silicon monoxide, and a processed derivative thereof.
7. The method according to claim 1, wherein the electrolyte to be evaluated comprises one or more of ionic liquid, organic liquid of lipid type, organic liquid of carbonate type, organic liquid of ether type, organic liquid of sulfone type or sulfoxide type, organic liquid of nitrile type, silicon-based electrolyte, phosphorus-based electrolyte, and their derivatives.
8. The method of claim 7, wherein,
the electrolyte to be evaluated further includes a lithium salt, which is a phosphorus element-containing lithium salt, a boron element-containing lithium salt, a nitrogen element-containing lithium salt, or an inorganic lithium salt.
9. The method according to claim 1, wherein in the micro-nano structure template cleaning step, the micro-nano structure template is washed with an organic solvent and dried, wherein the organic solvent is a volatile linear carbonate organic solvent.
10. The method according to claim 1, wherein in the micro-nano structure template analysis step, the set analysis is one or a combination of morphological analysis, elemental analysis, thermal analysis and mechanical analysis of the micro-nano structure template,
wherein, the appearance analysis is one or a combination of a plurality of scanning electron microscope analysis, a transmission electron microscope, an optical microscope and a scanning probe microscope;
wherein, the element analysis is one or a combination of more of an atomic emission spectrometer and an energy dispersion X-ray spectrometer;
wherein, the thermal analysis is one or a combination of more of differential thermal analysis, thermogravimetric analysis, differential scanning calorimetry analysis, static thermomechanical analysis and dynamic thermomechanical analysis;
wherein the mechanical analysis is atomic force microscopy analysis.
11. The method of claim 1, wherein the metal is lithium.
12. The method of claim 4, wherein the silicon has a single chemical composition, a single morphology, and a monomer size of regularly arranged micro-nano structures of 10nm to 1 um.
13. The method of claim 12, wherein the silicon has a single chemical composition, a single morphology, and a monomer size of regularly arranged micro-nano structures of 10nm to 500 nm.
14. The method according to claim 7, wherein the electrolyte is one or more of a linear carbonate organic electrolyte, a cyclic carbonate organic electrolyte, a linear ether electrolyte and a cyclic ether electrolyte, and derivatives thereof.
15. The method of claim 8, wherein,
the lithium salt is one or a mixture of more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium dioxalate borate, lithium bistrifluoromethanesulfonylimide and derivatives thereof.
16. The method of claim 8, wherein
The electrolyte to be evaluated further comprises an additive, wherein the additive is one or more of fluoro-carbonates, unsaturated organic electrolyte, silicon-based polymer, lithium salt, sodium salt, potassium salt and ionic liquid, and derivatives thereof.
17. The method of claim 9, wherein the organic solvent is dimethyl carbonate or diethyl carbonate.
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