CN103022451B - Nano silicon particles filled carbon nano tube compound as well as preparation method and application thereof - Google Patents
Nano silicon particles filled carbon nano tube compound as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN103022451B CN103022451B CN201210566788.3A CN201210566788A CN103022451B CN 103022451 B CN103022451 B CN 103022451B CN 201210566788 A CN201210566788 A CN 201210566788A CN 103022451 B CN103022451 B CN 103022451B
- Authority
- CN
- China
- Prior art keywords
- silicon
- silicon nanoparticle
- carbon nano
- cnt
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002041 carbon nanotube Substances 0.000 title abstract description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 title abstract description 6
- -1 carbon nano tube compound Chemical class 0.000 title abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 66
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000010703 silicon Substances 0.000 claims abstract description 59
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 59
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 48
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 42
- 238000011049 filling Methods 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 238000003860 storage Methods 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 55
- 239000007789 gas Substances 0.000 claims description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 22
- 238000009415 formwork Methods 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- 239000004411 aluminium Substances 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 13
- 229910000077 silane Inorganic materials 0.000 claims description 13
- 239000012159 carrier gas Substances 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 230000008602 contraction Effects 0.000 claims description 7
- 230000037427 ion transport Effects 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 241001012508 Carpiodes cyprinus Species 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005336 cracking Methods 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 abstract description 8
- 239000011856 silicon-based particle Substances 0.000 abstract 1
- 235000013339 cereals Nutrition 0.000 description 32
- 238000005229 chemical vapour deposition Methods 0.000 description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000006253 efflorescence Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 206010037844 rash Diseases 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005183 dynamical system Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the field of lithium ion battery cathode materials, in particular to a nano silicon particle filled carbon nano tube compound as well as a preparation method and an application thereof. According to the invention, the nano silicon particles can be filled in the carbon nano tube in a controlled manner, the filling amount and the size of the nano silicon particles can be precisely controlled, and the filled compound is used as high performance lithium ion battery cathode material. The weight ratio of the nano silicon particles can be precisely controlled within a range of 2-50 wt%, the size of the nano silicon particles can be precisely controlled in a range of 1-25 nm, and the size of carbon nano tube filled with the nano silicon particles is uniformly and precisely controlled in a range of 10-100 nm. Through controlled filling of the nano silicon particles in the hollow tube chamber of the carbon nano tube, the invention solves the problems that the silicon particle size is hard to control, and that the large volume expansion of silicon when used as the cathode of a lithium battery causes low coulombic efficiency, poor cycle performance and the like. When used as a lithium ion battery cathode material, the compound shows higher lithium storage capacity, higher coulombic efficiency and longer cycle life.
Description
Technical field
The present invention relates to lithium ion battery negative material field, be specially a kind of silicon nanoparticle and be filled in compound in CNT and its preparation method and application, by silicon nanoparticle at the loading of the intraluminal controlled filling of CNT hollow, silicon grain and size controllable precise, filled composite can be used as high performance lithium ionic cell cathode material.
Background technology
Lithium ion chargeable battery is as conventional energy storage device, for lead-acid battery and nickel-cadmium cell, there is higher voltage, high energy density, long service life, the features such as environmentally friendly and memory-less effect, have just played very important effect, have been widely used in the aspects such as moving electronic components, communication apparatus and stand-by power supply since commercialization.Along with the fast development of electric motor car and hybrid electric vehicle, lithium ion battery, due to the advantage of its uniqueness, is considered to the ideal candidates of the dynamical system of electric motor car.High power density, high energy density and long service life, become the problem that present stage lithium ion battery for electric vehicle research and development are the most in the urgent need to address.The performance of energy storage device depends on the performance of used material to a great extent.With regard to negative material, traditional graphite cathode is due to its lower theoretical specific capacity (372mAh/g), and be difficult to meet the application requirement improved constantly, therefore the high-capacity cathode material of Development of Novel becomes an important trend.Have the theoretical specific capacity of 4200mAh/g when silicon and lithium generation alloying reaction, it has become most potential lithium ion battery negative material of future generation.But, when silicon materials are used for lithium ion battery negative, due to lithium embedding with deviate to cause the volume generation acute variation (300-400%) of silicon, thus silicon is broken, efflorescence departing from electrode current collecting body, cause capacity attenuation fast.Therefore, effectively solve silicon for volumetric expansion problem during lithium ion battery negative, become one of hot issue of current lithium cell negative pole research.In recent years, along with rise and the development of nanosecond science and technology, nano material starts to play a significant role in electrochemical energy storage, namely by the nanometer structural design of material, improves the power density of lithium ion battery, energy density and cycle life.
CNT can regard the quasi-one-dimensional nanometer material that graphene sheet layer is curling as, excellent properties such as having good conductivity, chemical stability is high, intensity is high, pliability is good.Recent research shows, unique nanometer confinement effect of CNT hollow tube chamber, can ensure that being filled into hollow intraluminal storage lithium active matter is in nanoscale, and can the volumetric expansion of restricted activity thing when embedding lithium, prevent its efflorescence and peeling off when removal lithium embedded, thus make electrode keep higher capacity and good cyclical stability (document 1, Yong Wang, Minghong Wu, ZhengJiao, Jim Yang Lee, Chem.Mater.21:3210-3215 (2009) document 2, Yu, Wan-Jing, Hou, Peng-Xiang, Li, Feng, Liu, Chang J.Mater.Chem.22:13756-13763 (2010) document 3, Hongkun Zhang, Huaihe Song, Xiaohong Chen, Jisheng Zhou J.Phys.Chem.C 116:22774-22779 (2012)).But optionally silicon is filled in the hollow tube chamber of CNT and is difficult to operation, rarely have silicon selective filling so far at CNT hollow tube inner chamber and the report storing up lithium performance thereof.An only work (J.Am.Chem.Soc., 2010,132 (25), pp 8548-8549) be depositing silicon in the standby CNT of the anodic oxidation aluminium formwork legal system of 300nm at diameter, prepare coaxial carbon/silicone tube, and find that this compound has and excellent store lithium performance.But this super-large diameter CNT has not been suitable for research nano-scale three-dimensional effect, and what fill is coaxial silicone tube.Therefore, selective filling silicon grain in minor diameter (being less than 100nm) CNT, and realizing the accurate control of silicon loading and particle size, the research and development storing lithium performance impact and high performance lithium ionic cell cathode material to nano silicon particles to research CNT are significant.
Summary of the invention
The object of the present invention is to provide a kind of silicon nanoparticle filling carbon nano-pipe compound and its preparation method and application, silicon grain is controllably filled in CNT hollow tube chamber and is used for lithium cell negative pole, the problem such as solve the particle size being difficult at present control silicon and the coulombic efficiency caused for volumetric expansion large during lithium cell negative pole is low, cycle performance is poor.
Technical scheme of the present invention is:
A kind of silicon nanoparticle filling carbon nano-pipe compound, silicon nanoparticle is controllably filled in CNT hollow tube chamber, forms compound; Wherein, the controllable precise between 2-50wt% of the weight shared by silicon nanoparticle, size controllable precise within the scope of 1-25nm of silicon nanoparticle, is filled with hollow tube chamber internal diameter size even also controllable precise within the scope of 10-100nm of the CNT of silicon grain.
Described silicon nanoparticle filling carbon nano-pipe compound, preferably, weight shared by silicon nanoparticle controllable precise between 10-30wt%, size controllable precise within the scope of 5-15nm of silicon nanoparticle, is filled with size even also controllable precise within the scope of 30-60nm of the CNT of silicon grain.
The preparation method of described silicon nanoparticle filling carbon nano-pipe compound, there is the anodic alumina films of regular pore structure as template, in protective gas, by carbon geochemistry vapour deposition, first at the organic lower carbon number hydrocarbons deposited carbon layer of the inner surface cracking of the nano pore of anodic alumina films; Again using silane as silicon source, in protective gas, chemical vapor deposited silicon in aluminium oxide/carbon nano pore, thus evenly form silicon grain in anodised aluminium duct after deposited carbon layer; Finally remove anodic oxidation aluminium formwork, thus obtain the carbon mano-tube composite being filled with silicon grain in hollow tube chamber.
The preparation method of described silicon nanoparticle filling carbon nano-pipe compound, anodic alumina films is prepared by sulfuric acid or oxalic acid electrolysis, and its aperture is 10-100 nanometer, and length is 50 nanometer-200 microns, both ends open.
The preparation method of described silicon nanoparticle filling carbon nano-pipe compound; with protective gas: nitrogen, argon gas or helium are carrier gas; carbon geochemistry vapour deposition temperature is 600-900 DEG C; total gas couette is 100-500ml/min; wherein the volumetric concentration of organic lower carbon number hydrocarbons is 1-20%, and sedimentation time is 0.5-6 hour.
The preparation method of described silicon nanoparticle filling carbon nano-pipe compound, organic lower carbon number hydrocarbons is ethene, acetylene or propylene, and the thickness forming carbon-coating at the organic lower carbon number hydrocarbons of the inner surface cracking in the surface of anodic alumina films and duct is 5-20 nanometer.
The preparation method of described silicon nanoparticle filling carbon nano-pipe compound; with protective gas: nitrogen, argon gas, helium or hydrogen are carrier gas; chemistry of silicones vapour deposition temperature is 500-700 DEG C; total gas couette is 50-500ml/min; wherein the volumetric concentration of silane is 2-50%; sedimentation time is 2-30min, and deposition pressure is 1-760torr.
The application of described silicon nanoparticle filling carbon nano-pipe compound, to the carbon mano-tube composite of silicon nanoparticle be filled with as negative pole, be assembled into lithium ion battery, when this compound is used for lithium ion battery negative material, show higher lithium storage content, high coulombic efficiency and long circulation life, wherein lithium storage content is 500-2000mAh/g, coulombic efficiency > 95%, and cycle life is in 16-50 week.
The application of described silicon nanoparticle filling carbon nano-pipe compound, the lithium storage content that lithium ion battery is high, high coulombic efficiency, long circulation life are by the structures shape of this material, wherein silicon nanoparticle contributes high lithium storage content, and CNT hollow tube chamber and elastic tube wall provide space and the lithium ion transport passage of volumetric expansion and contraction for silicon grain.
The application of described silicon nanoparticle filling carbon nano-pipe compound, lithium ion can be transmitted by the carbon-coating of CNT wall, the elastic tube wall diameter expandable to 130% of CNT.
Advantage of the present invention is:
1, the invention provides a kind of by silicon nanoparticle in the intraluminal controlled filling of CNT hollow and the method being used for high performance lithium ionic cell cathode, can realize silicon grain is completely controllably filled in the hollow tube chamber of minor-diameter carbon nanotube, efficiently solve silicon volumetric expansion when embedding lithium, efflorescence departing from electrode current collecting body, and cause the problems such as fast capacity is decayed, coulombic efficiency difference.
2, the CNT that the silicon grain that prepared by the present invention is filled, content and the size of silicon accurately can be controlled by the reaction temperature, total gas flow rate, silane concentration and reaction time etc. when optimizing chemical vapour deposition (CVD), percentage by weight controllable precise between 2-50wt% of silicon grain, the size of silicon grain is controlled within the scope of 1-25nm.
3, the CNT of the controlled filling of silicon prepared of the inventive method, pure, free from admixture component, during for lithium ion battery negative, demonstrates the lithium storage content far above graphite cathode.
4, the present invention illustrates CNT hollow tube chamber and elastic tube wall for silicon grain provides space and the lithium ion transport passage of volumetric expansion and contraction, and lithium ion can be transmitted by the carbon-coating of CNT wall, the elastic tube wall of CNT is inflatable to 130%.
5, the present invention is using being filled with the carbon mano-tube composite of silicon nanoparticle as negative pole, is assembled into lithium ion battery, and its lithium storage content up to 1920mAh/g, can improve 5 times compared with the 372mAh/g of graphite negative electrodes, and has high coulombic efficiency and long circulation life.When the CNT of filling silicon grain is used for lithium ion battery negative material, show far above the lithium storage content of graphite cathode and higher coulombic efficiency and longer cycle life.
Accompanying drawing explanation
Fig. 1. the silicon nanoparticle of embodiment 1 is controlled is filled in the intraluminal transmission photo of CNT hollow.
Fig. 2. the silicon nanoparticle of embodiment 2 is controlled is filled in the intraluminal transmission photo of CNT hollow.
Fig. 3. the silicon nanoparticle of embodiment 2 CNT of filling is as the cycle performance curve of lithium ion battery negative material.
Fig. 4. the pure silicon nanoparticle of comparative example 1 is as the cycle performance curve of lithium ion battery negative material.
Detailed description of the invention
Below by embodiment in detail the present invention is described in detail.
Embodiment 1.
High-purity (purity is at more than 99.8wt%) aluminium flake with the oxalic acid solution of 3wt% for electrolyte, 20 DEG C, the condition anodic oxygenization of 40V the two ends perforate, the thickness that within 4 hours, prepare is 40 microns, aperture is that the anodic alumina films of 50 nanometers is as template.After anodic oxidation aluminium formwork drying, 650 DEG C of chemical vapour deposition (CVD)s carrying out acetylene 2 hours, using nitrogen as carrier gas, reacting gas total flow was 200ml/min, and the volumetric concentration of acetylene gas is 10%, and the thickness of deposited carbon layer is 6 nanometers.By the anodic oxidation aluminium formwork of deposit carbon 500 DEG C of chemical vapour deposition (CVD)s carrying out silane 5 minutes, using argon gas as carrier gas, reacting gas total flow is 50ml/min, and the volumetric concentration of silane is 2%.Adopt the phosphoric acid solution of 10wt% to be removed by the alumina formwork after siliceous deposits, just obtain silicon grain and be uniformly filled in the intraluminal CNT of hollow completely, the hollow tube chamber internal diameter size being filled with the CNT of silicon grain is 38 nanometers.As shown in Figure 1, the content of filling silicon is about 5wt%, and the Size Distribution of silicon grain is 3-8 nanometer, integrated distribution is in 6 nanometers, and for having the lithium storage content of 600mAh/g during lithium particle GND, coulombic efficiency is more than 95%, after circulating 16 weeks, its reversible capacity conservation rate is 99.7%.
In the present embodiment, the lithium storage content that lithium ion battery is high, high coulombic efficiency, long circulation life are by the structures shape of this material, wherein silicon nanoparticle contributes high lithium storage content, and CNT hollow tube chamber and elastic tube wall provide space and the lithium ion transport passage of volumetric expansion and contraction for silicon grain.Lithium ion transmits by the carbon-coating of CNT wall, and the elastic tube wall diameter of CNT is almost unchanged.
Embodiment 2.
The preparation method of anodic oxidation aluminium formwork is with embodiment 1.Difference is anodised voltage is 45V, the anodic oxidation aluminium formwork aperture prepared is: 65 nanometers, after alumina formwork drying, 700 DEG C of chemical vapour deposition (CVD)s carrying out ethene 2 hours, using nitrogen as carrier gas, reacting gas total flow is 200ml/min, and the volumetric concentration of ethylene gas is 5%, thickness 6 nanometer of deposited carbon layer.By the anodic oxidation aluminium formwork of deposit carbon 600 DEG C of chemical vapour deposition (CVD)s carrying out silane 20 minutes, using hydrogen as carrier gas, reacting gas total flow is 100ml/min, and the volumetric concentration of silane is 2%.Adopt the phosphoric acid solution of 10wt% to be removed by the alumina formwork after siliceous deposits, just obtain silicon grain and be uniformly filled in the intraluminal CNT of hollow completely.As shown in Figure 2, the hollow tube chamber internal diameter size being filled with the CNT of silicon grain is 53 nanometers, and the content of filling silicon is about 40%, and the Size Distribution of silicon grain is 18-22 nanometer, and integrated distribution is in 20 nanometers.As shown in Figure 3, for having the lithium storage content of 1650mAh/g during lithium particle GND, coulombic efficiency is more than 95%, and after circulating 16 weeks, its reversible capacity conservation rate is 99.1%.
In the present embodiment, the lithium storage content that lithium ion battery is high, high coulombic efficiency, long circulation life are by the structures shape of this material, wherein silicon nanoparticle contributes high lithium storage content, and CNT hollow tube chamber and elastic tube wall provide space and the lithium ion transport passage of volumetric expansion and contraction for silicon grain.Lithium ion transmits by the carbon-coating of CNT wall, the elastic tube wall diameter expandable to 130% of CNT.
Embodiment 3.
The preparation method of anodic oxidation aluminium formwork is with embodiment 1, difference is anodised voltage is 60V, the anodic oxidation aluminium formwork aperture prepared is: 100nm, after alumina formwork drying, 700 DEG C of chemical vapour deposition (CVD)s carrying out acetylene 2 hours, using argon gas as carrier gas, reacting gas total flow was 300ml/min, the volumetric concentration of acetylene gas is 10%, and the thickness of deposited carbon layer is 15 nanometers.By the anodic oxidation aluminium formwork of deposit carbon 550 DEG C of chemical vapour deposition (CVD)s carrying out silane 30 minutes, using hydrogen as carrier gas, reacting gas total flow is 50ml/min, and the volumetric concentration of silane is 5%.Adopt the phosphoric acid solution of 10wt% to be removed by the alumina formwork after siliceous deposits, just obtain silicon grain and be uniformly filled in the intraluminal CNT of hollow completely, the hollow tube chamber internal diameter size being filled with the CNT of silicon grain is 70nm.The content of filling silicon is about 50%, and the Size Distribution of silicon grain is 23-28 nanometer, and integrated distribution is in 25 nanometers, for having the lithium storage content of 1920mAh/g during lithium particle GND, coulombic efficiency is more than 95%, and after circulating 16 weeks, its reversible capacity conservation rate is 99%.
In the present embodiment, the lithium storage content that lithium ion battery is high, high coulombic efficiency, long circulation life are by the structures shape of this material, wherein silicon nanoparticle contributes high lithium storage content, and CNT hollow tube chamber and elastic tube wall provide space and the lithium ion transport passage of volumetric expansion and contraction for silicon grain.Lithium ion transmits by the carbon-coating of CNT wall, the elastic tube wall diameter expandable to 120% of CNT.
Embodiment 4.
High-purity (purity is at more than 99.8wt%) aluminium flake with the sulfuric acid solution of 10wt% for electrolyte, 10 DEG C, the condition anodic oxygenization of 20V prepares two ends perforate for 2 hours, thickness is 30 microns, aperture is that the anodic alumina films of 30 nanometers is as template.After anodic oxidation aluminium formwork drying, 800 DEG C of chemical vapour deposition (CVD)s carrying out ethene 1 hour, using nitrogen as carrier gas, reacting gas total flow was 300ml/min, and the volumetric concentration of ethylene gas is 2%, and the thickness of deposited carbon layer is 5 nanometers.By the anodic oxidation aluminium formwork of deposit carbon 700 DEG C of chemical vapour deposition (CVD)s carrying out silane 20 minutes, using argon gas as carrier gas, reacting gas total flow is 200ml/min, and the volumetric concentration of silane is 5%.Adopt the phosphoric acid solution of 10wt% to be removed by the alumina formwork after siliceous deposits, just obtain silicon grain and be uniformly filled in the intraluminal CNT of hollow completely, the hollow tube chamber internal diameter size being filled with the CNT of silicon grain is 20 nanometers.The content of filling silicon is about 18%, and the Size Distribution of silicon grain is 8-12 nanometer, and integrated distribution is in 10 nanometers, for having the lithium storage content of 1090mAh/g during lithium particle GND, coulombic efficiency is more than 95%, and after circulating 16 weeks, its reversible capacity conservation rate is 99.3%.
In the present embodiment, the lithium storage content that lithium ion battery is high, high coulombic efficiency, long circulation life are by the structures shape of this material, wherein silicon nanoparticle contributes high lithium storage content, and CNT hollow tube chamber and elastic tube wall provide space and the lithium ion transport passage of volumetric expansion and contraction for silicon grain.Lithium ion transmits by the carbon-coating of CNT wall, the elastic tube wall diameter expandable to 109% of CNT.
Comparative example 1.
Be the business silica flour of 20 nanometers when being used for lithium ion battery negative material by average grain diameter, it shows poor cycle life and coulombic efficiency, as shown in Figure 4.Although present the reversible capacity of 2600mAh/g first, its cyclical stability is very poor, and after circulation in 20 weeks, specific capacity sharp-decay, lower than the theoretical capacity of graphite cathode material 372mAh/g.
In this comparative example, the pure silicon nanoparticle of similar particle diameter but shows and diametrically oppositely stores lithium performance, demonstrates the confinement effect that CNT hollow tube chamber and elastic tube wall are providing silicon grain to store volumetric expansion in lithium process and shrink space further.
Embodiment result shows, nano silicon particles controllably can be filled in CNT hollow tube chamber by the preparation condition of control anodic oxidation aluminium formwork, the condition of chemical vapor carbon deposition, the condition of chemical vapor deposited silicon by the present invention, the content of silicon and particle size controllable precise.When this material is used for lithium ion battery negative material, demonstrates the lithium storage content far above graphite cathode and the coulombic efficiency far above pure silicon powder and cycle life, can be used as potential high performance lithium ionic cell cathode material of future generation.
Claims (9)
1. a silicon nanoparticle filling carbon nano-pipe compound, is characterized in that: silicon nanoparticle is controllably filled in CNT hollow tube chamber, forms compound; Wherein, the weight shared by silicon nanoparticle is controlled between 2-50 wt%, and the size of silicon nanoparticle is controlled within the scope of 1-25 nm, and the hollow tube chamber internal diameter size being filled with the CNT of silicon grain is even and controlled within the scope of 10-100 nm;
The preparation method of described silicon nanoparticle filling carbon nano-pipe compound, there is the anodic alumina films of regular pore structure as template, in protective gas, by carbon geochemistry vapour deposition, first at the organic lower carbon number hydrocarbons deposited carbon layer of the inner surface cracking of the nano pore of anodic alumina films; Again using silane as silicon source, in protective gas, chemical vapor deposited silicon in aluminium oxide/carbon nano pore, thus evenly form silicon grain in anodised aluminium duct after deposited carbon layer; Finally remove anodic oxidation aluminium formwork, thus obtain the carbon mano-tube composite being filled with silicon grain in hollow tube chamber.
2. according to silicon nanoparticle filling carbon nano-pipe compound according to claim 1, it is characterized in that: the weight shared by silicon nanoparticle is controlled between 10-30 wt%, the size of silicon nanoparticle is controlled within the scope of 5-15 nm, and the internal diameter size being filled with the CNT of silicon grain is even and controlled within the scope of 30-60 nm.
3. according to silicon nanoparticle filling carbon nano-pipe compound according to claim 1, it is characterized in that: anodic alumina films is prepared by sulfuric acid or oxalic acid electrolysis, and its aperture is 10-100 nanometer, and length is 50 nanometer-200 microns, both ends open.
4. according to silicon nanoparticle filling carbon nano-pipe compound according to claim 1; it is characterized in that: with protective gas: nitrogen, argon gas or helium are carrier gas; carbon geochemistry vapour deposition temperature is 600-900 oC; total gas couette is 100-500 ml/min; wherein the volumetric concentration of organic lower carbon number hydrocarbons is 1-20%, and sedimentation time is 0.5-6 hour.
5. according to silicon nanoparticle filling carbon nano-pipe compound according to claim 1, it is characterized in that: organic lower carbon number hydrocarbons is ethene, acetylene or propylene, the thickness forming carbon-coating at the organic lower carbon number hydrocarbons of the inner surface cracking in the surface of anodic alumina films and duct is 5-20 nanometers.
6. according to silicon nanoparticle filling carbon nano-pipe compound according to claim 1; it is characterized in that: with protective gas: nitrogen, argon gas, helium or hydrogen are carrier gas; chemistry of silicones vapour deposition temperature is 500-700 oC; total gas couette is 50-500 ml/min; wherein the volumetric concentration of silane is 2-50%; sedimentation time is 2-30 min, and deposition pressure is 1-760 torr.
7. according to the application of silicon nanoparticle filling carbon nano-pipe compound according to claim 1, it is characterized in that: will the carbon mano-tube composite of silicon nanoparticle be filled with as negative pole, be assembled into lithium ion battery, when this compound is used for lithium ion battery negative material, show higher lithium storage content, high coulombic efficiency and long circulation life, wherein lithium storage content is 500-2000 mAh/g, coulombic efficiency >95%, and cycle life is in 16-50 weeks.
8. according to the application of silicon nanoparticle filling carbon nano-pipe compound according to claim 7, it is characterized in that: the lithium storage content that lithium ion battery is high, high coulombic efficiency, long circulation life are by the structures shape of this material, wherein silicon nanoparticle contributes high lithium storage content, and CNT hollow tube chamber and elastic tube wall provide space and the lithium ion transport passage of volumetric expansion and contraction for silicon grain.
9. according to the application of silicon nanoparticle filling carbon nano-pipe compound according to claim 8, it is characterized in that: lithium ion can be transmitted by the carbon-coating of CNT wall, the elastic tube wall diameter expandable to 130% of CNT.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210566788.3A CN103022451B (en) | 2012-12-24 | 2012-12-24 | Nano silicon particles filled carbon nano tube compound as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210566788.3A CN103022451B (en) | 2012-12-24 | 2012-12-24 | Nano silicon particles filled carbon nano tube compound as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103022451A CN103022451A (en) | 2013-04-03 |
| CN103022451B true CN103022451B (en) | 2015-03-25 |
Family
ID=47970771
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210566788.3A Active CN103022451B (en) | 2012-12-24 | 2012-12-24 | Nano silicon particles filled carbon nano tube compound as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103022451B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104638252B (en) * | 2015-02-13 | 2017-04-12 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon composited negative electrode material, preparation method of silicon composited negative electrode material and lithium ion battery |
| CN106207108B (en) * | 2016-07-09 | 2018-07-27 | 太原理工大学 | Si-C composite material and the preparation method and application thereof based on macromolecule foaming microballoon |
| CN107623110B (en) * | 2016-07-15 | 2022-04-12 | 微宏动力系统（湖州）有限公司 | Silicon-based composite negative electrode material, preparation method and lithium ion secondary battery |
| CN106410204A (en) * | 2016-11-22 | 2017-02-15 | 天津赫维科技有限公司 | Preparation method of carbon nanotube/silicon cathode material |
| KR102115601B1 (en) * | 2017-03-16 | 2020-05-26 | 주식회사 엘지화학 | Structure |
| CN106981640A (en) * | 2017-05-11 | 2017-07-25 | 新疆大学 | A kind of novel cathode material for lithium ion battery iron titanate lithium/carbon composite nanotube |
| CN107323044B (en) * | 2017-06-23 | 2019-07-09 | 过冬 | A kind of preparation method of conductive paper/glass fiber flame retardant composite material |
| KR102207529B1 (en) * | 2018-03-14 | 2021-01-26 | 주식회사 엘지화학 | Amorphous silicon-carbon complex, manufacturing method thereof and lithium secondary battery comprising the same |
| CN109546108A (en) * | 2018-11-08 | 2019-03-29 | 中航锂电（洛阳）有限公司 | A kind of low bulk silicon based composite material and preparation method, silicon based anode material and lithium ion battery |
| CN111430690B (en) * | 2020-03-31 | 2021-11-23 | 中国汽车技术研究中心有限公司 | Self-supporting silicon/carbon nanotube composite anode material and preparation method thereof |
| CN113264713A (en) * | 2021-03-05 | 2021-08-17 | 成都佰思格科技有限公司 | Hard carbon-silicon composite negative electrode material and preparation method thereof |
| CN116936753A (en) * | 2022-03-29 | 2023-10-24 | 比亚迪股份有限公司 | Silicon-carbon electrode material and preparation method and application thereof |
| CN115448294B (en) * | 2022-09-16 | 2024-08-27 | 武汉市碳翁科技有限公司 | Method for preparing carbon nano tube and silicon composite film material by chemical gas phase flow reaction |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101745434A (en) * | 2008-12-19 | 2010-06-23 | 中国科学院金属研究所 | Method for selectively filling ferric oxide particles in hollow cavity of carbon nanotube |
| CN101962792A (en) * | 2009-07-24 | 2011-02-02 | 中国科学院金属研究所 | Method for preparing pore diameter controllable through hole anodized aluminum oxide film |
-
2012
- 2012-12-24 CN CN201210566788.3A patent/CN103022451B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101745434A (en) * | 2008-12-19 | 2010-06-23 | 中国科学院金属研究所 | Method for selectively filling ferric oxide particles in hollow cavity of carbon nanotube |
| CN101962792A (en) * | 2009-07-24 | 2011-02-02 | 中国科学院金属研究所 | Method for preparing pore diameter controllable through hole anodized aluminum oxide film |
Non-Patent Citations (2)
| Title |
|---|
| Deformations in Si-Li Anodes Upon Electrochemical Alloying in Nano-Confined Space;Benjamin Hertzberg等;《Journal of the American Chemical Society》;20100608;第132卷(第25期);第8548～8549页 * |
| Fe2O3纳米颗粒在碳纳米管中空管腔内的可控填充;侯鹏翔等;《第九届全国新型炭材料学术研讨会论文集》;20100618;第456～459页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103022451A (en) | 2013-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103022451B (en) | Nano silicon particles filled carbon nano tube compound as well as preparation method and application thereof | |
| Zhang et al. | MXene-based materials for electrochemical energy storage | |
| Shen et al. | Progress on lithium dendrite suppression strategies from the interior to exterior by hierarchical structure designs | |
| Mu et al. | A two-dimensional nitrogen-rich carbon/silicon composite as high performance anode material for lithium ion batteries | |
| Du et al. | Strategies to succeed in improving the lithium-ion storage properties of silicon nanomaterials | |
| Pan et al. | Facile synthesis of yolk–shell structured Si–C nanocomposites as anodes for lithium-ion batteries | |
| DiLeo et al. | Enhanced capacity and rate capability of carbon nanotube based anodes with titanium contacts for lithium ion batteries | |
| JP5594656B2 (en) | Method for producing positive electrode material of lithium ion secondary battery | |
| Chen et al. | Hollow mesoporous carbon spheres for high performance symmetrical and aqueous zinc-ion hybrid supercapacitor | |
| Tao et al. | Porosity controlled synthesis of nanoporous silicon by chemical dealloying as anode for high energy lithium-ion batteries | |
| CN102324501B (en) | Silicon-based cathode composite material for lithium ion battery and preparation method thereof | |
| Feng et al. | Three-dimensional ordered porous carbon for energy conversion and storage applications | |
| EP2387806A1 (en) | High efficiency energy conversion and storage systems using carbon nanostructured materials | |
| CN103985846B (en) | A kind of silicon nanoparticle structure of carbon load and its preparation method and application | |
| TW201135769A (en) | High performance carbon nanotube energy storage device | |
| CN105489394A (en) | Fabricating method for graphene nanometer wall based on electromagnetic field reinforced plasma chemical vapor deposition | |
| CN105705460A (en) | Method for preparing hollow silicon spheres as well as hollow silicon spheres prepared therefrom | |
| CN105679551A (en) | Ni(OH)2/NiO nanoparticle-based fabrication method for graphene nanowall supercapacitor electrode | |
| Khan et al. | SiO2-based lithium-ion battery anode materials: a brief review | |
| CN106025242A (en) | Silicon alloy nano-wire compound negative electrode material for lithium-ion battery and preparation method thereof | |
| CN108923037A (en) | Silicon-rich SiOx-C material and preparation method and application thereof | |
| CN101521273B (en) | In-situ synthesis method for preparing tin-carbon/core-shell nano-particle fully filled carbon nano-tube composite anode material | |
| CN101355150A (en) | Method for preparing graphitic carbon nanometer tube combination electrode material for lithium ion battery | |
| Yang et al. | A critical review of silicon nanowire electrodes and their energy storage capacities in Li-ion cells | |
| Zeng et al. | Hierarchically porous graphene/wood-derived carbon activated using ZnCl 2 and decorated with in situ grown NiCo 2 O 4 for high–performance asymmetric supercapacitors |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |