CN117810395A - Silicon-based negative electrode material, preparation method thereof and lithium ion battery - Google Patents
Silicon-based negative electrode material, preparation method thereof and lithium ion battery Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 57
- 239000010703 silicon Substances 0.000 title claims abstract description 57
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 12
- 239000007773 negative electrode material Substances 0.000 title claims description 14
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 92
- 239000010405 anode material Substances 0.000 claims abstract description 33
- 229920000768 polyamine Polymers 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 18
- 239000013067 intermediate product Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 150000001450 anions Chemical class 0.000 claims abstract description 6
- -1 silver hexafluorophosphate Chemical compound 0.000 claims description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 10
- 125000000129 anionic group Chemical group 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000011863 silicon-based powder Substances 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- IHRMYWSNDPZDBA-UHFFFAOYSA-N n,n,n',n'-tetramethyldecane-1,10-diamine Chemical compound CN(C)CCCCCCCCCCN(C)C IHRMYWSNDPZDBA-UHFFFAOYSA-N 0.000 claims description 4
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 claims description 4
- QROGIFZRVHSFLM-UHFFFAOYSA-N prop-1-enylbenzene Chemical class CC=CC1=CC=CC=C1 QROGIFZRVHSFLM-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- WNLYONPBCCQPHU-UHFFFAOYSA-N 1-ethenyl-4-(fluoromethyl)benzene Chemical compound FCC1=CC=C(C=C)C=C1 WNLYONPBCCQPHU-UHFFFAOYSA-N 0.000 claims description 3
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 claims description 3
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 3
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- SKCNNQDRNPQEFU-UHFFFAOYSA-N n'-[3-(dimethylamino)propyl]-n,n,n'-trimethylpropane-1,3-diamine Chemical compound CN(C)CCCN(C)CCCN(C)C SKCNNQDRNPQEFU-UHFFFAOYSA-N 0.000 claims description 3
- DMQSHEKGGUOYJS-UHFFFAOYSA-N n,n,n',n'-tetramethylpropane-1,3-diamine Chemical compound CN(C)CCCN(C)C DMQSHEKGGUOYJS-UHFFFAOYSA-N 0.000 claims description 3
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 3
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 claims description 3
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 238000005349 anion exchange Methods 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- VEAZEPMQWHPHAG-UHFFFAOYSA-N n,n,n',n'-tetramethylbutane-1,4-diamine Chemical compound CN(C)CCCCN(C)C VEAZEPMQWHPHAG-UHFFFAOYSA-N 0.000 claims 2
- 239000010410 layer Substances 0.000 abstract description 18
- 238000000576 coating method Methods 0.000 abstract description 13
- 239000002210 silicon-based material Substances 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052744 lithium Inorganic materials 0.000 abstract description 11
- 239000011241 protective layer Substances 0.000 abstract description 8
- 238000009830 intercalation Methods 0.000 abstract description 7
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000011856 silicon-based particle Substances 0.000 description 6
- 229920000620 organic polymer Polymers 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
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- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000000412 dendrimer Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
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- 238000005342 ion exchange Methods 0.000 description 2
- 238000005649 metathesis reaction Methods 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
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- 238000007086 side reaction Methods 0.000 description 2
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- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
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- 239000002131 composite material Substances 0.000 description 1
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- 239000011889 copper foil Substances 0.000 description 1
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Classifications
-
- 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 application discloses a silicon-based anode material, a preparation method and a lithium ion battery. The silicon-based anode material comprises particles and a shell layer coated on the surfaces of the particles, wherein the preparation raw materials of the shell layer comprise a compound I and a polyamine compound. The coating shell layer has good elasticity and mechanical strength and has the property of ionic liquid. The preparation method comprises the following steps: mixing a compound I with a silicon source, and adding a polyamine compound for reaction to obtain an intermediate product; and adding an anion replacement compound into the intermediate product for reaction, and drying to obtain the silicon-based anode material. The compound I with the dendritic multifunctional groups is used as a reaction raw material, so that a good coating network can be formed, in addition, the polybasic benzene ring of the compound I endows the organic protective layer with high mechanical strength, and the organic protective layer is combined with the polyamine compound with a soft alkyl chain as a main chain, so that the coating material can be endowed with good flexibility, thereby effectively limiting the expansion of the silicon material in the lithium intercalation process, and being beneficial to improving the battery performance.
Description
Technical Field
The application belongs to the technical field of battery materials, and particularly relates to a silicon-based negative electrode material, a preparation method and a lithium ion battery.
Background
Silicon material (Si) has a high theoretical specific capacity (4200 mAh.g) -1 ) The lithium intercalation potential and the reserve are rich, and the lithium intercalation potential and the reserve are considered as candidate materials of the negative electrode of the next generation Lithium Ion Battery (LIB). However, commercialization of silicon anodes has progressed slowly, mainly due to failure of the electrodes during cycling, including mechanical failure and electrochemical failure. Mechanical failure is caused by lithium intercalation expansion of the silicon material and can be avoided by reducing the size of the silicon material; while electrochemical failure is mainly related to solid electrolyte membranes (SEI films), the process of destroying and regenerating the SEI films during cycling consumes a large amount of active lithium and exacerbates side reactions of the electrolyte, resulting in rapid decay of cell performance.
Besides the preparation of nano silicon by reducing the particle size, the construction of the core-shell structure is a method capable of effectively reducing the expansion rate of the silicon-based material pole piece. In the prior art, the silicon coating using an inorganic material has a certain effect of suppressing the volume expansion, but the effect of suppressing the expansion is limited. Therefore, the silicon-based anode material is provided, so that the volume expansion of the silicon material is effectively inhibited, and the good electrochemical performance of the silicon material is ensured, and the technical problem to be solved is urgent.
Disclosure of Invention
The invention provides a silicon-based negative electrode material, a preparation method and a lithium ion battery, and aims to solve the problems that a negative electrode piece formed by the existing silicon-based material is high in expansion rate and the battery cycle performance is affected.
In one aspect, an embodiment of the present application provides a silicon-based anode material, including a particle and a shell layer coated on the surface of the particle, where a preparation raw material of the shell layer includes a compound I and a polyamine compound;
wherein the chemical formula of the compound I is as follows:
wherein X is any one of Cl or F.
In some embodiments, the mass ratio of the particles to the shell layer is (30-70): 1.
in some embodiments, the particles comprise at least one of silicon powder, a silicon oxygen material, or a silicon carbon material.
On the other hand, the embodiment of the application also provides a preparation method of the silicon-based anode material, which is used for preparing the silicon-based anode material in any embodiment, and the preparation method comprises the following steps:
mixing a compound I with a silicon source, and adding a polyamine compound for reaction to obtain an intermediate product;
and adding an anion replacement compound into the intermediate product for reaction, and drying to obtain the silicon-based anode material.
In some embodiments, the polyamine-based compound includes N, N, N ', N' -tetramethyl-1, 6-hexanediamine, N, N, N ', N' -tetramethyl-1, 10-decanediamine, 2,6, 10-trimethyl-2, 6, 10-triazaundecane, N, one of N, N ', N' -tetramethyl-1, 4-butanediamine, N, N, N ', N' -tetramethyl-1, 3-propanediamine, N, N, N ', N' -tetramethyl ethylenediamine or N, N, N, N, N-pentamethyl diethylenetriamine.
In some embodiments, the anionic replacement compound comprises one of hexafluorophosphoric acid, tetrafluoroboric acid, silver hexafluorophosphate, silver tetrafluoroborate, ammonium hexafluorophosphate, and ammonium tetrafluoroborate.
In some embodiments, the mass ratio of the silicon source, compound I, and polyamine compound is 1: (20-40): (0.25-0.6).
In some embodiments, the molar ratio of the anionic metathesis compound to the intermediate product is (6-7.2): 1.
in some embodiments, the compound I is mixed with the silicon source for a period of time ranging from 1 to 4 hours.
In some embodiments, the polyamine-based compound is added for a reaction time of 10 to 60 minutes.
In some embodiments, the reaction is carried out for a period of time ranging from 1 to 3 hours with the addition of the anionic displacement compound.
In some embodiments, the compound I is prepared by:
mixing para-halomethylstyrene, cuCl and pyridine in an organic solvent, heating and reacting to obtain the compound I.
In some embodiments, the molar ratio of halomethylstyrene, cuCl, and pyridine is 10: (1-1.2): (2-2.5).
In some embodiments, the concentration of the halomethylstyrene in the organic solvent is from 1g/3ml to 1g/5ml.
In some embodiments, the halomethylstyrene comprises p-chloromethylstyrene or p-fluoromethylstyrene.
In some embodiments, the organic solvent comprises chlorobenzene, dimethyl sulfoxide, N-methylpyrrolidone.
In some embodiments, the temperature of the heating is 100 to 125 ℃.
The embodiment of the application also provides a lithium ion battery, which comprises a negative electrode plate, wherein the negative electrode plate comprises a negative electrode current collector and a negative electrode active material layer arranged on the negative electrode current collector, and the negative electrode active material layer comprises a silicon-based negative electrode material in any embodiment.
The silicon-based anode material comprises particles and a shell layer coated on the surfaces of the particles, wherein the preparation raw materials of the shell layer comprise a compound I and a polyamine compound. Compared with the coating shell layer formed by inorganic materials, the coating shell layer has the characteristics of adjustable molecular weight and structure, has the property of ionic liquid and is beneficial to realizing the conduction of lithium ions. The preparation method of the silicon-based anode material provided by the application comprises the following steps: mixing a compound I with a silicon source, and adding a polyamine compound for reaction to obtain an intermediate product; and adding an anion replacement compound into the intermediate product for reaction, and drying to obtain the silicon-based anode material. According to the preparation method, the multifunctional dendritic compound I is used as a reaction raw material, so that a good coating network can be formed, in addition, the multi-element benzene ring of the compound I is endowed with high mechanical strength to the organic protective layer, and the compound I is combined with the polyamine compound with a soft alkyl chain as a main chain, so that the coating material can be endowed with good flexibility, thereby effectively limiting the expansion of the silicon material in the lithium intercalation process, and being beneficial to improving the battery performance.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below in connection with the embodiments of the present application. It will be apparent that the described embodiments are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application.
In the description of the present application, it should be noted that, unless explicitly specified and limited otherwise, the terms "connected," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically connected, electrically connected or can be communicated with each other; can be directly connected or indirectly connected through an intermediate medium, and can be communicated with the inside of two elements or the interaction relationship of the two elements. The specific meaning of the terms in this application will be understood by those of ordinary skill in the art as the case may be. In the description of the present application, the meaning of "a plurality" is two or more, unless explicitly defined otherwise. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more features.
The following disclosure provides many different embodiments, or examples, for implementing different structures of the application. In order to simplify the disclosure of the present application, the components and arrangements of specific examples are described below. Of course, they are merely examples and are not intended to limit the present application.
The first embodiment of the application provides a silicon-based anode material, which comprises particles and a shell layer coated on the surfaces of the particles, wherein the preparation raw materials of the shell layer comprise a compound I and a polyamine compound;
wherein, the chemical formula of the compound I is as follows:
wherein X is any one of Cl or F, and Jilv/Jifu in the compound I is a polyamine compound reaction site.
The silicon particles are easy to generate serious volume expansion phenomenon in the lithium intercalation process due to the influence of physical and chemical properties of the silicon particles, and are gradually crushed or even pulverized along with the battery core circulation, the pole piece conductive network is destroyed, in addition, the battery core SEI film consumes a large amount of active lithium in the process of destroying and regenerating in the circulation process and aggravates the side reaction of electrolyte, and the capacity of the battery core is rapidly attenuated. The compound I and the polyamine compound are subjected to nucleophilic substitution reaction to obtain quaternary ammonium salt, then the ionic liquid characteristic organic polymer is prepared through ion exchange reaction, the organic coating formed by the organic polymer has ionic liquid property, and the molecular weight and the structure can be regulated and controlled, so that the ionic liquid composite anode has elasticity and mechanical strength, the damage to silicon particles and a pole piece conductive network caused by the expansion of the silicon particles can be effectively inhibited, and the anode pole piece prepared by using the silicon-based anode material provided by the embodiment of the application has lower expansion rate and better cycle performance.
In some embodiments, the organic polymer forming the shell layerHas a molecular weight of 2X 10 4 ～12×10 4 g/mol. Because the compound I is a rigid compound and mainly provides strength for the protective layer, the polyamine compound is a flexible compound and improves toughness for the protective layer. When the silicon is embedded with lithium to generate volume expansion, the rigid section plays a role in binding particles, and when the silicon particles are delithiated and the volume is reduced, the toughness section controls the protection layer to rebound so as to prevent the pole piece conductive network from being disconnected. In addition, the protective layer has the function of an ion-like liquid, and ensures the rapid transmission of lithium ions between the protective layers. The molecular weight of the organic polymer meets the value range, and the formed protective layer has ideal effect on inhibiting the expansion of the silicon-based material.
In some embodiments, the mass ratio of particles to shell is (30-70): 1.
in some embodiments, the particles are selected from at least one of a silicon powder, a silicon oxygen material, or a silicon carbon material.
On the other hand, the embodiment of the application also provides a preparation method of the silicon-based anode material, which is used for preparing the silicon-based anode material in any embodiment, and the preparation method comprises the following steps:
mixing a compound I with a silicon source, and adding a polyamine compound for reaction to obtain an intermediate product;
adding an anion replacement compound into the intermediate product for reaction, and drying to obtain a silicon-based anode material;
the compound I and polyamine compound are subjected to nucleophilic substitution reaction to obtain quaternary ammonium salt, and then the organic polymer with ionic liquid characteristic is prepared through ion exchange reaction. The compound I is a multifunctional dendritic compound and is obtained after reacting with polyamine compounds, so that a good coating network can be formed; in addition, the polybasic benzene ring of the compound I endows the organic coating layer with high mechanical strength, the polyamine compound is a soft alkyl chain, and the organic coating layer is endowed with good flexibility, so that the expansion of the silicon material in the lithium intercalation process is effectively limited, and the battery performance is improved. The preparation process adopts an in-situ crosslinking method to coat the silicon material, so that the problem of poor dissolution in the process of crosslinking the polymer coating material can be effectively avoided.
In some embodiments, compound I is prepared by the steps of:
mixing para-halomethylstyrene, cuCl and pyridine in an organic solvent, heating and reacting to obtain the compound I.
Specifically, the preparation method of the silicon-based anode material provided in the embodiment may be implemented by the following steps:
s1, sequentially adding a certain amount of chlorobenzene, halogenated methyl styrene, cuCl and pyridine into a three-necked flask, uniformly mixing, vacuumizing and sealing, stirring the flask at a certain temperature for a certain time to react, cooling to room temperature after the reaction is finished, adding a certain amount of tetrahydrofuran into the cooled flask to the room temperature, stirring for a few hours, pouring a large amount of ethanol into the cooled flask to settle, dissolving the settled product into the tetrahydrofuran and the ethanol, repeatedly dissolving, settling for 3 times, and drying to obtain the compound I.
S2, adding silicon powder after dissolving the compound I, stirring for a certain time, then dropwise adding a certain amount of polyamine compound, and continuing stirring for reacting for a certain time to obtain a reaction solution containing an intermediate product.
S3, adding a certain amount of anion replacement compound into the reaction solution containing the intermediate product, stirring and reacting for a certain time, and then performing spray drying on the reaction solution to obtain the silicon-based anode material containing the polymer coating layer.
In some embodiments, the polyamine-based compound includes N, N, N ', N' -tetramethyl-1, 6-hexanediamine, N, N, N ', N' -tetramethyl-1, 10-decanediamine, 2,6, 10-trimethyl-2, 6, 10-triazaundecane, N, one of N, N ', N' -tetramethyl-1, 4-butanediamine, N, N, N ', N' -tetramethyl-1, 3-propanediamine, N, N, N ', N' -tetramethyl ethylenediamine or N, N, N, N, N-pentamethyl diethylenetriamine.
In some embodiments, the anionic replacement compound comprises one of hexafluorophosphoric acid, tetrafluoroboric acid, silver hexafluorophosphate, silver tetrafluoroborate, ammonium hexafluorophosphate, and ammonium tetrafluoroborate.
In some embodiments, the mass ratio of silicon source, compound I to polyamine compound is (20-40): 1: (0.25-0.6).
In some embodiments, the molar ratio of the anionic metathesis compound to the intermediate is (6-7.2): 1.
in some embodiments, the time for mixing compound I with the silicon source is 1-4 hours, it being understood that the time for mixing compound I with the silicon source (in h) may be any one or a range between any two of 1, 2, 3, 4.
In some embodiments, the reaction time for adding the polyamine compound is 10-60 min, and it is understood that the reaction time for adding the polyamine compound may take any one or any range between any two of 10, 20, 30, 40, 50, 60 (unit: min).
In some embodiments, the time for the reaction to proceed with the addition of the anionic displacement compound is 1 to 3 hours, it being understood that the time for the reaction to proceed with the addition of the anionic displacement compound may take any one of 1, 2, 3 or a range between any two of the values (unit: h).
In some embodiments, the molar ratio of halomethylstyrene, cuCl, and pyridine is 10: (1-1.2): (2-2.5).
In some embodiments, the concentration of halomethylstyrene in the organic solvent is from 1g/3ml to 1g/5ml.
In some embodiments, the halomethylstyrene comprises p-chloromethylstyrene or p-fluoromethylstyrene.
In some embodiments, the organic solvent comprises chlorobenzene, dimethyl sulfoxide, N-methylpyrrolidone.
In some embodiments, the heating temperature is 100-125 ℃, it being understood that the heating temperature can take on any one or range between any two of 100, 105, 110, 115, 120, 125 (in degrees c).
The embodiment of the application also provides a lithium ion battery, which comprises a negative electrode plate, wherein the negative electrode plate comprises a negative electrode current collector and a negative electrode active material layer arranged on the negative electrode current collector, and the negative electrode active material layer comprises a silicon-based negative electrode material in any embodiment.
The following description is made with reference to specific examples of the battery provided in the present application:
example 1
The embodiment provides a silicon-based anode material, which is prepared through the following steps:
s1, sequentially adding 15ml of chlorobenzene, 4.332g of p-chloromethyl styrene, 0.2594g of CuCl and 0.8706 pyridine into a three-necked flask, uniformly mixing, vacuumizing and sealing, heating the flask, reacting the reactants at 115 ℃, stirring for a certain time, cooling at room temperature, cooling to room temperature, adding 80ml of tetrahydrofuran, stirring for 2 hours, pouring a large amount of ethanol for sedimentation, adding the sediment product into tetrahydrofuran and ethanol for repeated dissolution, settling for 3 times, and vacuum drying at 60 ℃ to obtain the compound I.
S2, dissolving 4g of the compound I in 150ml of N-methylpyrrolidone, adding 120g of silicon powder, stirring for 2 hours, then dropwise adding 1.83g of N, N' -tetramethyl-1, 6-hexamethylenediamine, and stirring for 20 minutes to obtain a reaction solution containing an intermediate product.
S3, adding 4.56g of ammonium hexafluorophosphate into the reaction solution containing the intermediate product, stirring and reacting for 1.5h, and performing spray drying to obtain the silicon-based anode material containing the polymer coating layer.
Example 2
The material preparation procedure was the same as in example 1, increasing the silicon powder mass to only 200g.
Example 3
The material preparation procedure was the same as in example 1, except that 1.83g of N, N, N ', N' -tetramethyl-1, 6-hexamethylenediamine was replaced with N, N, N ', N' -tetramethyl-1, 10-decanediamine.
Example 4
The material preparation procedure was the same as in example 1, except that the stirring time after adding the silicon powder in step S2 was changed to 0.5h.
Example 5
The material preparation procedure was the same as in example 1, except that the stirring time after adding the polyamine compound to the silicon powder in step S2 was changed to 5 minutes.
Example 6
The material preparation procedure was the same as in example 1, substituting 4.56g of ammonium hexafluorophosphate with 4.56g of ammonium tetrafluoroborate.
Comparative example 1
The procedure was the same as in example 1, except that the reaction solution of the organic compound I and the polyamine-based compound in the coating process was replaced with an ethanol solution of the same mass.
The amounts of the reactants added in examples 1 to 6 and comparative example 1 are shown in Table 1.
TABLE 1
| Compound I | Solvent(s) | Silicon source | Polyamine compound | Anionic replacement compounds | |
| Example 1 | 4g | 150ml | 120g | 1.83g | 4.56 |
| Example 2 | 4g | 150ml | 200g | 1.83g | 4.56 |
| Example 3 | 4g | 150ml | 120g | 1.83g | 4.56 |
| Example 4 | 4g | 150ml | 120g | 1.83g | 4.56 |
| Example 5 | 4g | 150ml | 120g | 1.83g | 4.56 |
| Example 6 | 4g | 150ml | 120g | 1.83g | 4.56 |
The relevant reaction parameters in examples 1 to 6 and comparative example 1 are shown in Table 2.
TABLE 2
The silicon-based anode materials provided in examples 1 to 6 and comparative example 1 were prepared into button cells, and were subjected to full-charge expansion and electrochemical performance test analysis, specifically as follows:
preparing a button cell:
(1) Preparing a negative electrode plate: graphite, silicon-based material, carbon black and binder material were mixed at 72:24:1:3 weight ratio, and dispersing in deionized water to form uniform slurry. The slurry was then cast onto copper foil by doctor blade method and dried at 70 ℃. And then cold pressing, trimming and cutting, and drying for 12 hours at 100 ℃ under vacuum condition to obtain the negative electrode plate.
(2) Assembling 2032 type button half cell in a glove box filled with inert gas, wherein H 2 O and O 2 The content of (2) is less than 0.1ppm. The metal lithium sheet is used as a counter electrode, the PP/PE is used as a diaphragm, and 1M LiPF is used 6 (EC: EMC: dmc=1:1:1vol%) +3% fec (fluoroethylene carbonate) was used as the electrolyte.
Performance test:
(1) Cycle performance test
Each of the above-prepared batteries was taken 3 pieces each, and the battery was repeatedly charged and discharged through the following steps, and the discharge capacity retention rate of the battery was calculated.
First, in an environment of 25 ℃, 0.5C was discharged to 5V, 0.05C was discharged to 5V, 0.02C was discharged to 5V, 0.01C was discharged to 5mV, and then 0.1C was charged to 1.5V, and the charge specific capacity of the first cycle was recorded. Then, 200 cycles of discharging and charging were performed, and the specific charge capacity at the 200 th cycle was recorded. According to the following formula:
cyclic capacity retention = first cyclic specific capacity/200 th cyclic specific capacity x 100%,
the average capacity retention after cycling of each group of cells was calculated.
(2) Thickness expansion rate test for fully embedded state of negative pole piece
The thickness of the negative electrode plate before the assembled battery is measured and recorded as D 0 . Battery to be assembledIn the environment of 25 ℃, 0.1C is firstly discharged to 5mV, and 0.02C is firstly discharged to 5mV, so that the negative electrode plate is in a fully embedded state. Disassembling the battery, testing the thickness of the fully embedded negative electrode plate, and marking as D 1 The thickness of the foil used was 9. Mu.m. According to the following formula:
thickness expansion ratio= (D 1 -D 0 )/(D 0 -9)*100％。
The test results are shown in Table 3.
TABLE 3 Table 3
From the above results, the silicon-based anode material provided by the embodiment of the application effectively limits the expansion of silicon particles in the circulation process due to the existence of the organic coating shell layer, and improves the ionic conduction rate of the pole piece, so that the battery has better circulation performance.
The silicon-based anode material, the preparation method and the lithium ion battery provided by the embodiment of the application are described in detail, and specific examples are applied to the application to explain the principle and the implementation mode of the application, and the description of the above examples is only used for helping to understand the technical scheme and the core idea of the application; those of ordinary skill in the art will appreciate that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.
Claims (10)
1. The silicon-based anode material is characterized by comprising particles and a shell layer coated on the surfaces of the particles, wherein the shell layer is prepared from a raw material comprising a compound I and a polyamine compound;
wherein the chemical formula of the compound I is as follows:
wherein X is any one of Cl or F.
2. The silicon-based anode material according to claim 1, wherein the mass ratio of the particles to the shell layer is (30-70): 1.
3. a silicon-based anode material as defined in claim 1, wherein the particles comprise at least one of silicon powder, a silicon oxygen material, or a silicon carbon material.
4. A method for producing a silicon-based anode material as claimed in any one of claims 1 to 3, comprising the steps of:
mixing a compound I with a silicon source, and adding a polyamine compound for reaction to obtain an intermediate product;
and adding an anion replacement compound into the intermediate product for reaction, and drying to obtain the silicon-based anode material.
5. The method for preparing a silicon-based anode material according to claim 4, wherein the polyamine compound comprises N, N, N ', N' -tetramethyl-1, 6-hexamethylenediamine, N, N, N ', N' -tetramethyl-1, 10-decanediamine, 2,6, 10-trimethyl-2, 6, 10-triazaundecane, N, N, N ', N' -tetramethyl-1, 4-butanediamine, N, N, N ', N' -tetramethyl-1, 3-propanediamine, N, N, N ', one of N' -tetramethyl ethylenediamine or N, N, N, N, N-pentamethyl diethylenetriamine; and/or the number of the groups of groups,
the anion exchange compound includes one of hexafluorophosphoric acid, tetrafluoroboric acid, silver hexafluorophosphate, silver tetrafluoroborate, ammonium hexafluorophosphate, and ammonium tetrafluoroborate.
6. The method for preparing a silicon-based anode material according to claim 4, wherein,
the mass ratio of the silicon source, the compound I and the polyamine compound is (20-40): 1: (0.25 to 0.6); and/or the number of the groups of groups,
the molar ratio of the anionic substitution compound to the intermediate product is (6-7.2): 1.
7. the method for preparing a silicon-based anode material according to claim 4, wherein,
the mixing time of the compound I and the silicon source is 1-4 h; and/or the number of the groups of groups,
the reaction time of adding the polyamine compound is 10-60 min; and/or the number of the groups of groups,
the time for the reaction by adding the anion exchange compound is 1-3 h.
8. The method for preparing a silicon-based anode material according to claim 4, wherein the compound I is prepared by:
mixing para-halomethylstyrene, cuCl and pyridine in an organic solvent, heating and reacting to obtain the compound I.
9. The method for preparing a silicon-based anode material according to claim 8, wherein,
the molar ratio of the halogenated methyl styrene to the CuCl to the pyridine is 10: (1-1.2): (2-2.5); and/or the number of the groups of groups,
the concentration of the halogenated methyl styrene in the organic solvent is 1g/3 ml-1 g/5ml; and/or the number of the groups of groups,
the halogenated methyl styrene comprises p-chloromethyl styrene or p-fluoromethyl styrene; and/or the number of the groups of groups,
the organic solvent comprises chlorobenzene, dimethyl sulfoxide and N-methyl pyrrolidone; and/or the number of the groups of groups,
the heating temperature is 100-125 ℃.
10. A lithium ion battery comprising a negative electrode tab, wherein the negative electrode tab comprises a negative electrode current collector and a negative electrode active material layer disposed on the negative electrode current collector, the negative electrode active material layer comprising the silicon-based negative electrode material of claims 1-3 or comprising the silicon-based negative electrode material produced by the production method of any one of claims 4-9.
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