CN107425180A - Three-dimensional grapheme/silicon compound system, its preparation method and application - Google Patents
Three-dimensional grapheme/silicon compound system, its preparation method and application Download PDFInfo
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- CN107425180A CN107425180A CN201610348681.XA CN201610348681A CN107425180A CN 107425180 A CN107425180 A CN 107425180A CN 201610348681 A CN201610348681 A CN 201610348681A CN 107425180 A CN107425180 A CN 107425180A
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of three-dimensional grapheme/silicon compound system, its preparation method and application.The preparation method can include：Transition metal simple substance and/or compound containing transition metal and nano silicon particles is compound, reduced afterwards in reducing atmosphere high temperature, three-dimensional porous metallic catalyst template/silicon compound system is made, recycle chemical vapour deposition technique, the growing three-dimensional graphene on the compound system, three-dimensional grapheme/silicon compound system with catalyst backbone is obtained, performs etching processing afterwards, obtains three-dimensional grapheme/silicon composite granule.Not only bulk effect is small, electronic conductivity is high, pliability is strong for three-dimensional grapheme/silicon compound system of the present invention, also there is excellent heat conduction and mechanical property, it is with a wide range of applications, especially when applied to lithium ion battery negative material, can be under conditions of electrode capacity be ensured, the cycle life and stability of battery are improved, and its preparation technology is simple, efficiency high, is adapted to extensive implement.
Description
Technical field
Present invention relates particularly to a kind of three-dimensional grapheme/silicon compound system, its preparation method and application, belong to field of nanometer technology and new energy application field.
Background technology
Silicon materials are because having highest theoretical specific capacity (4200mAhg-1), moderate de-/intercalation potential (0.02~0.6V vs.Li/Li+), safe, cost is low and advantages of environment protection, turn into one of lithium ion battery negative material of great application prospect.But silicium cathode still be present, as bulk effect is huge
(- 320%), electronic conductivity low (~2.5 × 10-4 S·m-1) etc., so as to limit its application.
The content of the invention
It is a primary object of the present invention to provide a kind of three-dimensional grapheme/silicon compound system, its preparation method and application, to overcome deficiency of the prior art.
To realize aforementioned invention purpose, the technical solution adopted by the present invention includes：
The embodiments of the invention provide a kind of preparation method of three-dimensional grapheme/silicon compound system, it includes：
Transition metal simple substance and/or compound containing transition metal and nano silicon particles is compound, high temperature reductions are carried out in 400~1000 DEG C in reducing atmosphere afterwards, three-dimensional porous metallic catalyst template/silicon compound system is made；
Using chemical vapour deposition technique, the growing three-dimensional graphene on the three-dimensional porous metallic catalyst template/silicon compound system, three-dimensional grapheme/silicon compound system with catalyst backbone is obtained；
Processing is performed etching to the three-dimensional grapheme with the catalyst backbone/silicon compound system, obtains three-dimensional grapheme/silicon composite granule.
The embodiments of the invention provide a kind of preparation method of three-dimensional grapheme/silicon compound system, it includes：
Using transition metal simple substance and/or the compound containing transition metal is as raw material, and carries out high temperature reduction in 400~1000 DEG C in reducing atmosphere, and three-dimensional porous metallic catalyst template is made；
Using chemical vapour deposition technique, the growing three-dimensional graphene in the three-dimensional porous metallic catalyst template, the three-dimensional grapheme with catalyst backbone is obtained；
Processing is performed etching to the three-dimensional grapheme with catalyst backbone, obtains three-dimensional grapheme powder；
Three-dimensional grapheme powder and nano silicon particles is compound, obtain three-dimensional graphite/silicon composite granule.
The embodiment of the present invention additionally provides the three-dimensional grapheme/silicon compound system prepared by foregoing any method.
The embodiment of the present invention additionally provides the purposes of the three-dimensional grapheme/silicon compound system, such as prepares the purposes in lithium ion battery.
Compared with prior art, advantages of the present invention includes：
（1）Not only bulk effect is small, electronic conductivity is high, pliability is strong for a kind of three-dimensional grapheme/silicon compound system provided by the invention, also there is excellent heat conduction and mechanical property, it is with a wide range of applications, especially when applied to lithium ion battery negative material, under conditions of electrode capacity is ensured, the cycle life and stability of battery can be improved.
（2）The preparation method of three-dimensional grapheme/silicon compound system provided by the invention a kind of is simple to operate, efficiency high, is adapted to extensive implement.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of three-dimensional grapheme in the embodiment of the present invention 2/silicon compound system.
Fig. 2 is typical graphite alkene/cyclic curve figure of the silicon compound system as negative electrode of lithium ion battery prepared in 1-4 of the embodiment of the present invention.
Embodiment
In view of deficiency of the prior art, inventor is able to propose technical scheme through studying for a long period of time and largely putting into practice.The technical scheme, its implementation process and principle etc. will be further explained as follows.It is understood, however, that within the scope of the present invention, it can be combined with each other between each technical characteristic of the invention and each technical characteristic specifically described in below (eg embodiment), so as to form new or preferable technical scheme.As space is limited, no longer tire out one by one herein and state.
A kind of preparation method for three-dimensional grapheme/silicon compound system that the one side of the embodiment of the present invention provides includes：
Transition metal simple substance and/or compound containing transition metal and nano silicon particles is compound, high temperature reductions are carried out in 400~1000 DEG C in reducing atmosphere afterwards, three-dimensional porous metallic catalyst template/silicon compound system is made；
Using chemical vapour deposition technique, the growing three-dimensional graphene on the three-dimensional porous metallic catalyst template/silicon compound system, three-dimensional grapheme/silicon compound system with catalyst backbone is obtained；
Processing is performed etching to the three-dimensional grapheme with the catalyst backbone/silicon compound system, obtains three-dimensional grapheme/silicon composite granule.
Further, in the three-dimensional porous metallic catalyst template/silicon compound system, the contents of nano silicon particles is 1wt%~10wt%, and particle diameter is the nm of 10 nm~200, and the content of metallic catalyst is 90wt%~99wt%.
A kind of preparation method for three-dimensional grapheme/silicon compound system that the other side of the embodiment of the present invention provides includes：
Using transition metal simple substance and/or the compound containing transition metal is as raw material, and carries out high temperature reduction in 400~1000 DEG C in reducing atmosphere, and three-dimensional porous metallic catalyst template is made；
Using chemical vapour deposition technique, the growing three-dimensional graphene in the three-dimensional porous metallic catalyst template, the three-dimensional grapheme with catalyst backbone is obtained；
Processing is performed etching to the three-dimensional grapheme with catalyst backbone, obtains three-dimensional grapheme powder；
Three-dimensional grapheme powder and nano silicon particles is compound, obtain three-dimensional graphite/silicon composite granule.
Preferably, the preparation method includes：By three-dimensional grapheme powder and nano silicon particles in liquid phase environment it is compound, dry afterwards, obtain three-dimensional graphite/silicon composite granule.
Among some embodiments, the transition metal includes the combination of any one or more in Fe, Cu, Co, Ni, Pt or Ru, but not limited to this.
Among some embodiments, the compound containing transition metal includes any one or two or more combinations in transition metal oxide, transition metal salt or transition metal hydrate, but not limited to this.
Among some preferred embodiments, for the growth temperature used in the chemical vapour deposition technique for 400~1200 DEG C, growth time is 30s~2h, and growth pressure is the torr of 1 torr~800, and growth atmosphere includes hydrogen and/or argon gas etc., and not limited to this.
More preferable, the growth atmosphere used in the chemical vapour deposition technique includes hydrogen and/or argon gas etc., and not limited to this.
Further, the carbon source used in the chemical vapour deposition technique includes the combination of any one or more in solid phase, liquid phase or gas phase carbon source.
Wherein, the solid-phase carbon source includes the combination of any one or more in polymethyl methacrylate, Kynoar, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene, polyethylene glycol, dimethyl silicone polymer, glucose, sucrose, fructose or cellulose, and not limited to this.
Wherein, the phase carbon source includes the combination of any one or more in methanol, ethanol, propyl alcohol or aromatic hydrocarbon, and not limited to this.
Wherein, the gas phase carbon source includes the combination of any one or more in methane, acetylene, ethene, ethane, propane, carbon monoxide or carbon dioxide, and not limited to this.
Further, the number of plies that the graphene formed is grown by the chemical vapour deposition technique is 1~20 layer.
Among some embodiments, the preparation method may also include：Under extraneous subsidiary conditions, grow to form the three-dimensional grapheme using chemical vapour deposition technique；The extraneous subsidiary conditions include any one in microwave, condition of plasma, and not limited to this.
Among some preferred embodiments, the reducing atmosphere includes hydrogen or hydrogen and inert gas.
Preferably, the reducing atmosphere is mainly 0~500 by flow-rate ratio：10~1000 argon gas and hydrogen composition.
Among some embodiments, the preparation method may also include：Three-dimensional grapheme powder, nano silicon particles and dispersant, coupling agent liquid phase is compound, dry and obtain three-dimensional graphite/silicon composite granule.
Further, the preparation method can include：Nano silicon particles are dispersed in the organic solvent containing dispersant, add coupling agent afterwards, the nano silicon particles dispersion liquid is formed after being sufficiently mixed.The process can be carried out at ambient temperature, naturally it is also possible under the conditions of other suitable temperatures.
Wherein, described dispersant may be selected from but be not limited to polyvinylpyrrolidone, any of polyvinyl alcohol, polyethylene glycol, butadiene-styrene rubber, sodium carboxymethylcellulose, cetyl ammonium bromide, dodecyl sodium sulfate, neopelex, Kynoar, polytetrafluoroethylene (PTFE), Triton-100, tween, Tego Dispers610s or two or more combinations.
Wherein, described organic solvent may be selected from but be not limited to isopropanol, DBE（Dibasic ester）, ethyl carbitol acetate, butyl carbitol, butyl carbitol acetate, butyl cellosolve acetate, absolute ethyl alcohol, terpinol, dimethyl succinate, propylene glycol methyl ether acetate, dimethyl glutarate, N, any of dinethylformamide, DMA, 1-METHYLPYRROLIDONE, butyl glycol ether, ethylene glycol ether acetate, butanol, toluene, dimethylbenzene, dibutyl phthalate or two or more combinations.
Wherein, the coupling agent may be selected from but be not limited to titanate coupling agent, the combination of any one or more in silane coupler or aluminate coupling agent, but not limited to this.
Among some embodiments, the preparation method may also include：Processing is performed etching to the three-dimensional grapheme with catalyst backbone using wet corrosion technique, such as etching solution, obtains three-dimensional grapheme powder.
Wherein, the etching solution includes any one in hydrochloric acid, nitric acid, iron chloride, ferric nitrate, ammonium persulfate, Marble reagents, sulfuric acid or two or more combinations.For example, the concentration of the etching solution can be 0.05-6 M.
The embodiment of the present invention another aspect provides the three-dimensional grapheme/silicon compound system prepared by foregoing any method.
Further, the piece footpath of three-dimensional grapheme is 0.5~50 μm in the compound system, and thickness is the nm of 0.34 nm~10, and porosity is 60%~90%, and the particle diameter of nano silicon particles is 10 nm~200
Nm, and the content of nano silicon particles is 10wt%~95wt% in the compound system, and the content of three-dimensional grapheme is 1wt%~90wt%.
The embodiment of the present invention another aspect provides the purposes of the three-dimensional grapheme/silicon compound system, such as the purposes in lithium ion battery or lithium ion battery negative material is prepared.
The embodiment of the present invention another aspect provides a kind of lithium ion battery negative material, it includes described three-dimensional grapheme/silicon compound system.
The present invention is cross-linked to form tridimensional network using the graphene film of two dimension by space（That is three-dimensional grapheme）, with excellent conduction, heat conduction and mechanical property, and in the electric conductivity that can not only increase silicon after compound with silicon, can also effectively limit bulk effect of the silicon materials in lithium cell negative pole cyclic process.Three-dimensional grapheme/silicon compound system of the present invention under conditions of electrode capacity is ensured, can greatly improve the cycle life and stability of battery when being applied to negative electrode of lithium ion battery as active material.
Technical scheme is described in detail with reference to specific embodiment and accompanying drawing.
Embodiment 1 ：20g nickel chloride is put into tube furnace, 600 DEG C of 10 min of holding, atmosphere is：Hydrogen：300 sccm, argon gas：100 sccm.Tube furnace is raised to 1000 DEG C again, keeps 10 min at 1000 DEG C, now atmosphere is：Methane：30 sccm, hydrogen：200
Sccm, argon gas：200 sccm.Quartz ampoule is taken out and is cooled to room temperature.Use 1M
FeCl3/ 0.1M HCl are performed etching, and finally give three-dimensional grapheme powder.0.5g nano silica fumes, 0.05g polyvinylpyrrolidones and 0.01g Silane coupling agent KH550s are added to ultrasonic 1h in 10gN- first class pyrrolidones, three-dimensional grapheme is immersed in above solution after 30min, takes out drying, obtains three-dimensional grapheme/silicon compound system.
Embodiment 2 ：After 20g nickel chlorides and 0.5g nano silicon particles ground and mixeds 0.5h, it is put into tube furnace, 600 DEG C of 10 min of holding, atmosphere is：Hydrogen：300 sccm, argon gas：100 sccm.Tube furnace is raised to 1000 DEG C again, keeps 10 min at 1000 DEG C, now atmosphere is：Methane：30 sccm, hydrogen：200
Sccm, argon gas：200 sccm.Quartz ampoule is taken out and is cooled to room temperature.Use 3M
HCl is performed etching, washing, after drying, obtains three-dimensional grapheme/silicon compound system（Such as Fig. 1）.
Embodiment 3 ：20g nickel chloride is put into tube furnace, 600 DEG C of 10 min of holding, atmosphere is：Hydrogen：300 sccm, argon gas：100 sccm.Tube furnace is raised to 800 DEG C of 10 min of holding again, now atmosphere is：Methane：30 sccm, hydrogen：200 sccm, argon gas：200 sccm, air pressure are 100 Torr.Quartz ampoule is taken out and is cooled to room temperature.With 1M FeCl3/0.1M
HCl is performed etching, and finally gives three-dimensional grapheme powder.At room temperature by 0.5g nano silica fumes, 0.02g SDS（Lauryl sodium sulfate）Ultrasonic 1h in ethanol is added to 0.01g silane couplers KH570, three-dimensional grapheme is immersed in above solution after 30min, takes out drying, obtains three-dimensional grapheme/silicon compound system.
Embodiment 4 ：20g nickel chloride is put into tube furnace, 600 DEG C of 10 min of holding, atmosphere is：Hydrogen：300 sccm, argon gas：100 sccm.Tube furnace is raised to 900 DEG C again, keeps 10 min at 900 DEG C, now atmosphere is：Methane：30 sccm, hydrogen：200
Sccm, argon gas：200 sccm.Quartz ampoule is taken out and is cooled to room temperature.Use 3M
HCl is performed etching, and washing, finally gives three-dimensional grapheme powder.1g nano silica fumes and 0.01g titanate coupling agents are added to ultrasonic 1h in DMA at room temperature, three-dimensional grapheme is immersed in above solution after 30min, takes out drying, obtains three-dimensional grapheme/silicon compound system.
Using obtained exemplary three-dimensional graphene/silicon compound system product in above-described embodiment 1-4 as lithium ion battery negative material, negative plate is prepared into by collector of nickel foam, positive pole uses lithium piece, uses 1mol/L LiPF6Three component mixed solvent EC：DMC：EMC=1：1：1, v/v solution is electrolyte, and microporous polypropylene membrane is barrier film, is assembled into
CR2016 simulated batteries.Cycle performance test carries out constant current charge-discharge experiment using 0.1A/g electric current, and charging/discharging voltage is limited in 0~2.5 V, is tested in normal temperature condition, as a result as shown in Figure 2.
It should be understood that; the technology contents and technical characteristic of the present invention have revealed that as above; but those skilled in the art are still potentially based on teachings of the present invention and announcement and make a variety of replacements and modification without departing substantially from spirit of the present invention; therefore; the scope of the present invention should be not limited to the content disclosed in embodiment; and various replacements and modification without departing substantially from the present invention should be included, and covered by present patent application claim.
Claims (12)
- A kind of 1. preparation method of three-dimensional grapheme/silicon compound system, it is characterised in that including：Transition metal simple substance and/or compound containing transition metal and nano silicon particles is compound, high temperature reductions are carried out in 400~1000 DEG C in reducing atmosphere afterwards, three-dimensional porous metallic catalyst template/silicon compound system is made；Using chemical vapour deposition technique, the growing three-dimensional graphene on the three-dimensional porous metallic catalyst template/silicon compound system, three-dimensional grapheme/silicon compound system with catalyst backbone is obtained；Processing is performed etching to the three-dimensional grapheme with the catalyst backbone/silicon compound system, obtains three-dimensional grapheme/silicon composite granule.
- A kind of 2. preparation method of three-dimensional grapheme/silicon compound system, it is characterised in that including：Using transition metal simple substance and/or the compound containing transition metal is as raw material, and carries out high temperature reduction in 400~1000 DEG C in reducing atmosphere, and three-dimensional porous metallic catalyst template is made；Using chemical vapour deposition technique, the growing three-dimensional graphene in the three-dimensional porous metallic catalyst template, the three-dimensional grapheme with catalyst backbone is obtained；Processing is performed etching to the three-dimensional grapheme with catalyst backbone, obtains three-dimensional grapheme powder；Nano silicon particles and coupling agent are uniformly mixed to form nano silicon particles dispersion liquid in organic solvent, and the three-dimensional grapheme powder is mixed with the nano silicon particles homogeneous dispersion, is dried afterwards, obtains three-dimensional graphite/silicon composite granule.
- 3. preparation method according to claim 1 or 2, it is characterised in that：The transition metal includes Fe, Cu, Co, Ni, Pt or Ru；And/or the compound containing transition metal includes any one in transition metal oxide, transition metal salt or transition metal hydrate or two or more combinations；And/or the growth temperature used in the chemical vapour deposition technique is 400~1200 DEG C, growth time is 30s~2h, and growth pressure is the torr of 1 torr~800, and growth atmosphere includes hydrogen and/or argon gas.
- 4. preparation method according to claim 1, it is characterised in that：The content of nano silicon particles is 1wt%~10wt% in the three-dimensional porous metallic catalyst template/silicon compound system, and the content of metallic catalyst is 90wt%~99wt%, and the particle diameters of the nano silicon particles is the nm of 10 nm~200.
- 5. preparation method according to claim 3, it is characterised in that：The growth atmosphere used in the chemical vapour deposition technique includes hydrogen and/or argon gas；The carbon source used in the chemical vapour deposition technique includes solid phase, liquid phase or gas phase carbon source；Wherein, the solid-phase carbon source includes any one in polymethyl methacrylate, Kynoar, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene, polyethylene glycol, dimethyl silicone polymer, glucose, sucrose, fructose or cellulose or two or more combinations；The phase carbon source includes any one or two or more combinations in methanol, ethanol, propyl alcohol or aromatic hydrocarbon；The gas phase carbon source includes any one or two or more combinations in methane, acetylene, ethene, ethane, propane, carbon monoxide or carbon dioxide；And/or by the chemical vapour deposition technique grow the graphene formed the number of plies be 1~20 layer.
- 6. preparation method according to claim 1 or 2, it is characterised in that the preparation method includes：Under extraneous subsidiary conditions, grow to form the three-dimensional grapheme using chemical vapour deposition technique, wherein the extraneous subsidiary conditions include any one in microwave, condition of plasma；And/or the reducing atmosphere includes hydrogen or hydrogen and inert gas；Preferably, the reducing atmosphere is mainly 0~500 by flow-rate ratio：10~1000 argon gas and hydrogen composition.
- 7. preparation method according to claim 2, it is characterised in that also include：Nano silicon particles are dispersed in the organic solvent containing dispersant, add coupling agent afterwards, are thoroughly mixed to form the nano silicon particles dispersion liquid.
- 8. preparation method according to claim 7, it is characterised in that：The dispersant includes any of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, butadiene-styrene rubber, sodium carboxymethylcellulose, cetyl ammonium bromide, dodecyl sodium sulfate, neopelex, Kynoar, polytetrafluoroethylene (PTFE), Triton-100, tween, Tego Dispers610s or two or more combinations；And/or, the organic solvent includes isopropanol, DBE, ethyl carbitol acetate, butyl carbitol, butyl carbitol acetate, butyl cellosolve acetate, absolute ethyl alcohol, terpinol, dimethyl succinate, propylene glycol methyl ether acetate, dimethyl glutarate, N, any of dinethylformamide, DMA, 1-METHYLPYRROLIDONE, butyl glycol ether, ethylene glycol ether acetate, butanol, toluene, dimethylbenzene, dibutyl phthalate or two or more combinations；And/or the coupling agent includes any one in titanate coupling agent, silane coupler or aluminate coupling agent or two or more combinations.
- 9. preparation method according to claim 1, it is characterised in that including：Processing is performed etching to the three-dimensional grapheme with catalyst backbone using etching solution, obtains three-dimensional grapheme powder；Wherein, the etching solution includes any one in hydrochloric acid, nitric acid, iron chloride, ferric nitrate, ammonium persulfate, Marble reagents, sulfuric acid or two or more combinations.
- 10. three-dimensional grapheme/silicon compound system prepared by the method as any one of claim 1-9, it is characterised in that：The piece footpath of three-dimensional grapheme is 0.5~50 μm in the compound system, thickness is the nm of 0.34 nm~10, porosity is 60%~90%, the particle diameter of nano silicon particles is the nm of 10 nm~200, and the content of nano silicon particles is 10wt%~95wt% in the compound system, and the content of three-dimensional grapheme is 1wt%~90wt%.
- 11. three-dimensional grapheme described in claim 10/silicon compound system is in preparing the purposes in lithium ion battery or lithium ion battery negative material.
- 12. a kind of lithium ion battery negative material, it is characterised in that include the three-dimensional grapheme described in claim 10/silicon compound system.
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| CN117059790A (en) * | 2023-10-12 | 2023-11-14 | 中国科学院宁波材料技术与工程研究所 | Integrated battery assembly and preparation method and application thereof |
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