CN107539990A - A kind of porous silicon nano material and its production and use - Google Patents
A kind of porous silicon nano material and its production and use Download PDFInfo
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- CN107539990A CN107539990A CN201610587321.5A CN201610587321A CN107539990A CN 107539990 A CN107539990 A CN 107539990A CN 201610587321 A CN201610587321 A CN 201610587321A CN 107539990 A CN107539990 A CN 107539990A
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- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 79
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title description 4
- 239000000463 material Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 230000000694 effects Effects 0.000 claims abstract description 15
- 239000005046 Chlorosilane Substances 0.000 claims abstract description 13
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012190 activator Substances 0.000 claims abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 8
- 239000011777 magnesium Substances 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- 229910004721 HSiCl3 Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical class CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- 229910003910 SiCl4 Inorganic materials 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 4
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical group Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 4
- 229910007245 Si2Cl6 Inorganic materials 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 claims description 3
- 150000003222 pyridines Chemical class 0.000 claims description 3
- -1 pyroles Chemical class 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 3
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- 206010011224 Cough Diseases 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000002808 molecular sieve Substances 0.000 claims 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052799 carbon Inorganic materials 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000010189 synthetic method Methods 0.000 abstract description 4
- 230000003321 amplification Effects 0.000 abstract description 3
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 2
- 239000007787 solid Substances 0.000 description 29
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 229910019752 Mg2Si Inorganic materials 0.000 description 16
- 238000001291 vacuum drying Methods 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000010703 silicon Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000005119 centrifugation Methods 0.000 description 9
- 238000005229 chemical vapour deposition Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000002336 sorption--desorption measurement Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- 229910021332 silicide Inorganic materials 0.000 description 5
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000002153 silicon-carbon composite material Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910017623 MgSi2 Inorganic materials 0.000 description 2
- 229910019443 NaSi Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229960003638 dopamine Drugs 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003233 pyrroles Chemical class 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 150000003613 toluenes Chemical class 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- 229910010084 LiAlH4 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910003251 Na K Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 229910007264 Si2H6 Inorganic materials 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 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
Abstract
The invention discloses a kind of preparation method of porous silicon nano material, by chlorosilane under activator effect, room temperature at 200 DEG C in anhydrous organic solvent with after silication reactive magnesium, being prepared with mesoporous and bigger serface porous silicon nano material.It is of the invention compared with traditional synthetic method, it is simple to operate, reaction condition is gentle, yield is high, be easy to amplification synthesis, cost is cheap.The negative material for being used as lithium ion battery after the processing of bag carbon by the porous silicon nano material that the inventive method obtains has very high energy density and very excellent cycle performance.
Description
Technical field
The invention belongs to field of nanometer material technology, and in particular to a kind of preparation method of porous silicon nano material, i.e., by metal
Silicide and chlorosilane react in a solvent, are prepared with mesoporous and bigger serface porous silicon nano material, and
It is used as lithium ion battery negative material or as molecular screen material, the application in absorption, separation, catalysis, medical field.
Background technology
In recent years, the lithium ion battery based on Si negative materials has obtained extensive concern, and main advantage is Si negative poles
Theoretical capacity have great lifting compared with traditional graphite cathode（~4000 mAh g-1 vs. ~370 mAh g-1）.But
Si negative poles Volume Changes during embedding de- lithium are more than 300%, and caused result is easily active material is come off from electrode,
Secondly the stability of the solid liquid interface passivating film formed during electric discharge first in material surface can be destroyed, so as to shorten battery
Service life cycle.In order to solve this problem, research in recent years is typically intended to the size micron or nanometer of Si materials
Change and improve the cycle life of battery, because with the reduction of Si scantlings, the space increased between particle can be effective
Eliminate the influence of stress caused by Volume Changes.In addition, nano material has more avtive spots, lithium ion can be improved
Diffusion rate [Z. Chen, C. Wang, J. Lopez, Z.D. Lu, Y. Cui, Z.N. Bao,Adv. Energy. Mater. 2015, 5, 1401826; N. Lin, Y. Han, L.B. Wang, J.B. Zhou, J. Zhou, Y.C.
Zhu, Y.T. Qian, Angew. Chem. Int. Ed. 2015, 54, 3822; C. Wang, H. Wu, Z.
Chen, M. T. McDowell, Y. Cui, Z. N. Bao, Nat. Chem. 2013, 5, 1042]。
Simple substance silicon nano material uses chemical vapour deposition technique mostly（CVD）Prepare, i.e., using SiCl4, SiH4, Si2H6
It is raw material Deng volatile materials, in high temperature（>500°C）Or predecessor is decomposed and obtained under the conditions of laser irradiation etc..Solution legal system
The method of standby simple substance silicon nano material includes thermal decomposition of silane in supercritical solution and prepares silicon nanowires and nano-particle [J. D.
Holmes, K. P. Johnston, R. C. Doty, B. A. Korgel, Science, 2000, 287, 1471]、
Utilize metallic sodium or potassium, the LiAlH of strong reducing property4, metal silicide NaSi, MgSi2Deng reduction SiCl4, alkyl silane RSiH3
Or Si (OC2H5)4Etc. preparing silicon nano dots [M. Rosso-Vasic, E. Spruijt, B. van Lagen, L. De
Cola, H. Zuilhof, Small 2008, 4, 1835；R. A. Bley, S. M. Kauzlarich,J. Am. Chem. Soc. 1996, 118, 12461；D. Neiner, H. W. Chiu, S. M. Kauzlarich,J. Am. Chem. Soc. 2006, 128, 11016；H. Ma, F. Cheng, J. Chen, J. Zhao, C. Li, Z. Tao,
J. Liang, Adv. Mater. 2007, 19, 4067] etc..But this method usually requires harsh synthesis condition, production
Amount is very low, and typically can only obtain single Si quantum dots.Porous silicon nano material is passed through using monocrystalline silicon
Dry or wet etch acquisition [P. Granitzer, K. Rumpf,Materials 2010, 3, 943].It can also utilize
Inorganic salts carry out synthesizing porous silicon as hard template method, such as the SiO of metal Mg reduction specific morphologies is utilized under high temperature2Generate porous
Silicon [Z. Bao, M. R. Weatherspoon, S. Shian, Y. Cai, P. D. Graham, S. M. Allan,
G. Ahmad, M. B. Dickerson, B. C. Church, Z. Kang, H. W. Abernathy III, C. J.
Summers, M. Liu, K. H. Sandhage, Nature 2007, 446, 172]；Reduced under high temperature using metal Mg
Sodium metasilicate generation porous silicon [J. Liang, D. Wei, N. Lin, Y. Zhu, X. Li, J. Zhang, L. Fan,
Y. Qian, Chem. Commun. 2014, 50, 6856]；SiCl is reduced with Na-K alloys4Generation porous silicon [F. Dai,
J. Zai, R. Yi, M. L. Gordin, H. Sohn, S. Chen, D. Wang, Nat. Commun. 2014, 5,
3605] etc..Up to the present, the synthetic method of simple substance silicon nano material, which is very limited, is formed on harsh synthesis condition, as high temperature,
High pressure, anhydrous and oxygen-free operation and extremely active material such as Na, K, LiAlH4, silane, NaSi etc..Therefore, behaviour how is passed through
Make synthetic method that is easy, being easy to amplification come Si nano materials are prepared is still problem urgently to be resolved hurrily.
The content of the invention
The purpose of the present invention is the metal silicide Mg based on commercialization2Si and chlorosilane are raw material, develop a kind of letter
Just the method for synthesizing porous silicon nano material.Different from the method for some the synthesizing porous silicon or nano silicon material that have been reported,
Chemical solution method of the present invention based on routine, by activated dose of activation of metal silicide, and chlorosilane is in anhydrous organic solvent
Reaction, obtains having mesoporous porous silicon nano material.Further, can be by adding surfactant in reaction system
Obtain that there is bigger serface and regular mesoporous porous silica material.By using chemical vapour deposition (CVD), solwution method or water
Heat treatment method, organic hydrocarbon molecule, organic amine or sucrose or glucose cladding, carbonization are deposited on prepared porous silicon nanometer
Material surface, the negative pole that gained porous silicon-carbon composite is used as lithium ion battery show excellent chemical property.
Scheme is specific as follows used by the present invention solves its technical problem：
A kind of preparation method of porous silicon nano material, it is characterised in that by chlorosilane under activator effect, room temperature is to 200 DEG C
Under in anhydrous organic solvent with after silication reactive magnesium, reaction product passes through water or acid solution wash, is dried to obtain unbodied
Porous silicon nano material, the activator are ammonia, organic amine, pyroles, pyridines, one kind in imidazoles material or several
Kind.
Above-mentioned preparation method, the chlorosilane are SiCl4, HSiCl3, Si2Cl6In one or more.
Above-mentioned preparation method, the preferred NH of activator3, pyrroles, pyridine, N- methylimidazoles, triethylamine, Tri-n-Propylamine,
One or more in tri-n-butylamine, dibutyl amine or butylamine.
It is preferred that the mol ratio of chlorosilane and activator is 1：0.4, it is 12-24 hours preferably with the reaction time of activator.
The temperature of above-mentioned preparation method, chlorosilane and silication reactive magnesium is room temperature to 200 DEG C, preferably room temperature, i.e. 20-25
℃。
Above-mentioned preparation method, the anhydrous organic solvent are the one or more in hydrocarbon, halogenated hydrocarbons, ether, ester, preferably dichloro
Methane, Isosorbide-5-Nitrae-dioxane, tetrahydrofuran, toluene, the one or more in N- methylimidazoles.It is preferred that chlorosilane with it is anhydrous organic
Solvent ratios are 1/40（V/V）.
Above-mentioned preparation method, the use of water or acid solution wash is conventional treatment means, it is therefore an objective to solvable inorganic salts are removed,
The preferred inorganic acid of acid, such as sulfuric acid, hydrochloric acid, phosphoric acid.
The preparation method of porous silicon nano material of the present invention, in addition to further by being added in reaction system
Surfactant, it is made with the mesoporous porous silica material of bigger serface and rule.The surfactant is chain alkyl
The saturation of surfactant, preferably C8-C30 or undersaturated direct-connected or side chain alkyl surfactants, further preferred C8-
C18 saturation or undersaturated direct-connected or side chain alkyl surfactants, more preferably Cetyltrimethylammonium bromide, 16
One or more in alkyl trimethyl ammonium bromide, DTAB.
The preparation method of porous silicon nano material of the present invention, in addition to further by unbodied porous silicon nanometer
Material high temperature Crystallizing treatment under an ar atmosphere, or will reaction product first under an ar atmosphere after high temperature Crystallizing treatment again by water or
Acid solution wash, drying, the porous silicon nano material with mesopore orbit crystallized.The temperature of high temperature Crystallizing treatment, one
As be 600 ~ 800 DEG C.
Another object of the present invention is to provide a kind of porous silicon nano material, by chlorosilane under activator effect, room
Temperature at 200 DEG C in anhydrous organic solvent with after silication reactive magnesium, reaction product passes through water or acid solution wash, is dried to obtain
Silicon nano material, specific surface area are 150 ~ 250 m2 g-1, there is the duct of two kinds of different pore sizes, aperture is 2-4 nm and 20-30
nm.When reaction system adds surfactant, obtaining silicon nano material and have a well-regulated mesopore orbit, specific surface area is 400 ~
450 m2 g-1, aperture is 2-4 nm.
A preferred embodiment of the invention, the specific preparation method of above-mentioned porous silicon nano material are as follows：By mol ratio
For 1:0.4 HSiCl3The anhydrous CH of about 20 times of liquor capacities is added to Tri-n-Propylamine solution2Cl2In, room temperature magnetic agitation 12
After hour, addition and HSiCl3Mol ratio 1:1 Mg2Si, react at room temperature 8-24 hours.Obtained brown ceramic powder directly uses pickling
Solvable inorganic salts are washed away, obtain the unbodied porous silicon nano material with mesopore orbit.Or obtained brown powder
High temperature Crystallizing treatment after 30 minute, solvable inorganic salts is removed with acid elution, are crystallized under Ar atmosphere after the drying at end
Porous silicon nano material with mesopore orbit.
It is another object of the present invention to provide a kind of carbon coating porous silicon on the basis of porous silicon nano material is obtained to receive
Nano composite material, using chemical vapour deposition (CVD), solwution method or hydro-thermal treatment method, by organic hydrocarbon molecule, organic amine or sugarcane
Sugar or glucose cladding, carbonization are deposited on prepared porous silicon nano-material surface.Preferably, carbon is used as using benzene or toluene
Source, it is carbonized using the coated porous silicon nano material of chemical vapour sedimentation method, or selects the coated porous silicon nanometer of dopamine
Material is carbonized at 500 DEG C ~ 800 DEG C, or coated porous silicon nano material is carbonized under hydrothermal conditions with glucose.
A preferred embodiment of the invention, above-mentioned carbon coating porous silicon nano composite material, its preparation method mainly divide
Two steps, are concretely comprised the following steps：
（1）It is 1 by mol ratio:0.4 HSiCl3The anhydrous CH of 20 times of liquor capacities is added to Tri-n-Propylamine solution2Cl2In,
Room temperature magnetic agitation.After stirring 12-24 hours, addition and HSiCl3Mol ratio 1:1 Mg2Si, react at room temperature 8-24 hours.
After 30 minutes, solvable inorganic salts are removed with acid elution to the brown ceramic powder arrived for high temperature Crystallizing treatment under Ar atmosphere after the drying,
The porous silicon nano material with mesopore orbit crystallized.
（2）Will（1）In obtained porous silicon nano material toluene is pyrolyzed by CVD method, plate last layer on its surface
Carbon material, the porous silicon-carbon composite are used as the negative material of lithium battery.
It is a further object of the present invention to provide porous silicon nano material of the present invention to prepare negative electrode of lithium ion battery
Purposes in material.
It is a further object of the present invention to provide carbon coating porous silicon nano composite material of the present invention prepare lithium from
Purposes in sub- cell negative electrode material.
The main advantage of the present invention is：
（1）With the metal silicide Mg of commercialization2Si and chlorosilane are raw material, develop a kind of chemistry for being easy to industrialized production
Solwution method prepares porous silicon nano material.Compared with traditional synthetic method, this method is simple to operate, reaction condition is gentle,
Yield is up to 85%, is easy to amplification synthesis, and cost is cheap；
（2）The porous silicon nano material obtained by this invention has the mesopore orbit that aperture is 2~50 nm, and specific surface area is
150~450 m2 g-1, after the processing of bag carbon as lithium ion battery negative material with very high energy density and very
Excellent cycle performance；
（3）Obtain, with the mesoporous porous silicon nano material of rule, comparing surface by adding surfactant in reaction system
Product is 400 ~ 450 m2 g-1, aperture is 2-4 nm, can be used as molecular screen material, have in fields such as absorption, separation, catalysis, medical treatment
And be widely applied.
Brief description of the drawings
Fig. 1 is MgSi2Scanning electron microscope (SEM) photograph.
Fig. 2 is the X-ray powder diffraction figure for the porous silicon that embodiment 1 obtains.
Fig. 3 is the scanning electron microscope (SEM) photograph for the porous silicon that embodiment 1 obtains.
Fig. 4 is the N for the porous silicon that embodiment 1 obtains2Adsorption desorption curve and graph of pore diameter distribution.
Fig. 5 is that the porous silica material that embodiment 1 obtains encloses charging and discharging curve as preceding the two of lithium cell cathode material.
Fig. 6 is charge and discharge cycles data of the obtained porous silica material of embodiment 1 as lithium cell cathode material.
Fig. 7 is the N for the porous silicon that embodiment 10 obtains2Adsorption desorption curve and graph of pore diameter distribution.
Embodiment
Illustrate the specific steps of the present invention by the following examples, but be not limited by the example.
Used term in the present invention, unless otherwise indicated, typically there are those of ordinary skill in the art generally to manage
The implication of solution.
The present invention is described in further detail with reference to specific embodiment and with reference to data.It should be understood that the embodiment is
In order to demonstrate the invention, rather than the scope that limit the invention in any way.
In the examples below, the various processes and method not being described in detail are conventional methods as known in the art.
With reference to specific embodiment, the present invention is further described.
Embodiment 1
The first step：By 1 mL Tri-n-Propylamines and 1.1 mL HSiCl3It is added to the anhydrous CH of 40 mL2Cl2In, it is stirred at room temperature overnight.
Add 1 g Mg2Si（Mg2Si stereoscan photograph is shown in Fig. 1, blocks of solid, without special pattern）, stirring is anti-at room temperature
Answer 10 hours.Centrifugation, chloroform 3 ~ 4 times, vacuum drying, obtain brown solid.
Second step：Obtained brown solid is placed on and is connected with the tube furnace of high-purity Ar gas, with 15 DEG C of min-1Heating speed
Rate is heated to 700 DEG C and kept for 30 minutes.After Temperature fall, obtained solid is washed with 1 M HCl, then washed with distillation
Wash for several times, vacuum drying, obtain about 0.5 g（Yield 74%）The porous silicon nano material of yellowish-brown.Fig. 2 is the porous silicon nanometer material
The X-ray powder diffraction figure of material, the silicon materials that high-temperature process obtains as seen from the figure are crystal formation elemental silicon.Fig. 3 is the porous silicon
Scanning electron microscope (SEM) photograph, can be intuitive to see from scanning electron microscope (SEM) photograph the material on pattern with raw material Mg2Si has obvious poor
It is different.Fig. 4 is the N of the porous silicon2Adsorption desorption curve and graph of pore diameter distribution, from N2Adsorption desorption curve and pore size distribution curve can be seen
Go out, the material specific surface area is 190 m2 g-1, show obvious mesopore orbit（The nm of aperture about 3.8 and 24 nm）.
3rd step：Method by obtained porous silicon nano material by CVD, by the use of toluene as carbon source, plated on its surface
The graphited carbon in last layer part（800 DEG C, 15 minutes）, obtain porous silicon-carbon composite.
4th step：Porous silicon-the carbon composite and electrically conductive graphite, sodium carboxymethylcellulose that will be obtained in 3rd step
（CMC）In mass ratio 8:1:1 is modulated into slurry, and coated on copper foil, 80 DEG C are dried in vacuum overnight, and lithium battery electrode plate is made.
By the use of button lithium battery CR2025 as simulated battery, electrolyte composition is 1 M LiPF6（Ethylene carbonate：Diethyl carbonate=
1:1 volume ratio）, polypropylene screen is barrier film, and lithium piece is to electrode.
The battery for making to obtain to the step 4 of embodiment 1 is in 0.1 A g-1Current density, voltage range 0.01-1.5 V
Under the conditions of it is preceding two circle charging and discharging curve it is as shown in Figure 5.The mA h g of first circle specific discharge capacity ~ 4167 as shown in Figure 5-1, charge ratio
The mA h g of capacity ~ 3400-1, first charge-discharge coulombic efficiency ~ 81%.Fig. 6 is business silica flour（325 mesh）, the step of the embodiment of the present invention 1
Porous silico-carbo (PSi C) prepared by rapid two porous silicons (PSi) prepared and the step 2 of embodiment 1 is with 0.5 A g-1Electric current
The specific capacity of density cycle charge-discharge.By figure it can be seen that business Si powder after the circulation of several circles capacity with regard to rapid decrease,
Specific capacity is only 180 mA h g after the circle of circulation 20-1, decay 97%.And the porous Si that the present invention obtains has on cyclical stability
And be obviously improved, capacity is 1650 mA h g after the circle of circulation 50-1, decay 35%.After with CVD bag carbon, what is obtained is porous
Silico-carbo composite shows excellent stable circulation performance, and capacity is kept approximately constant after the circle of discharge and recharge 100, discharge and recharge
Specific capacity is stable in 2700 mA h g-1Left and right.
Embodiment 2
By 1.1 mL HSiCl3It is added to the anhydrous CH of 40 mL2Cl2In, it is stirred at room temperature overnight.Add 1 g Mg2Si, stir at room temperature
Mix reaction 48 hours.Centrifugation, chloroform 3 ~ 4 times, vacuum drying, obtained gray solid is unreacted Mg2Si and a small amount of
(about 20 mg, yield is less than Si nano-particles 10%).Compared with Example 1, in the case where lacking activator, can not obtain
Porous silicon nano material with mesopore orbit.
Embodiment 3
By 1 mL tri-n-butylamines and 1.1 mL HSiCl3It is added to the anhydrous CH of 40 mL2Cl2In, it is stirred at room temperature overnight.Add 1 g
Mg2Si, at room temperature stirring reaction 12 hours.Centrifugation, chloroform 3 ~ 4 times, vacuum drying, obtain brown solid.
Obtained brown solid is placed on and is connected with the tube furnace of high-purity Ar gas, with 15 DEG C of min-1Heating rate
To 700 DEG C and kept for 30 minutes.After Temperature fall, obtained solid is washed with 1 M HCl, then with distillation water washing number
It is secondary, vacuum drying, obtain the porous silicon nano material of about 0.5 g yellowish-brown crystallization.The x-ray powder of the porous silicon nano material
Diffraction patterns are basically identical with Fig. 2.Nitrogen adsorption test result shows that the material specific surface area is 185 m2 g-1, display is substantially
Mesopore orbit（The nm of aperture about 3.5 and 25 nm）.The battery performance with reference to made from the step of embodiment 1 the 3rd and four-step method with
The effect of embodiment 1 is essentially identical.
Embodiment 4
By the M NH of 10 mL 0.531,4- dioxane solutions and 1.1 mL HSiCl3It is added to the anhydrous 1,4- dioxies of 30 mL
In six rings, it is stirred at room temperature overnight.Add 1 g Mg2Si, at room temperature stirring reaction 12 hours.Centrifugation, chloroform 3 ~ 4 times, very
Sky is dried, and obtains brown solid.
Obtained brown solid is placed on and is connected with the tube furnace of high-purity Ar gas, with 15 DEG C of min-1Heating rate
To 700 DEG C and kept for 30 minutes.After Temperature fall, obtained solid is washed with 1 M HCl, then with distillation water washing number
It is secondary, vacuum drying, obtain the porous silicon nano material of about 0.5 g yellowish-brown crystallization.The x-ray powder of the porous silicon nano material
Diffraction patterns are basically identical with Fig. 2.Nitrogen adsorption test result shows that the material specific surface area is 150 m2 g-1, display is substantially
Mesopore orbit（The nm of aperture about 2.2 and 30 nm）.The battery performance with reference to made from the step of embodiment 1 the 3rd and four-step method with
The effect of embodiment 1 is essentially identical.
Embodiment 5
By 1 mL pyridines and 0.8 mL Si2Cl6It is added to the anhydrous CH of 40 mL2Cl2In, it is stirred at room temperature overnight.Add 1 g
Mg2Si.Stirring reaction 12 hours at room temperature.Centrifugation, chloroform 3 ~ 4 times, vacuum drying, obtain brown solid.
Obtained brown solid is placed on and is connected with the tube furnace of high-purity Ar gas, with 15 DEG C of min-1Heating rate
To 700 DEG C and kept for 30 minutes.After Temperature fall, obtained solid is washed with 1 M HCl, then with distillation water washing number
It is secondary, vacuum drying, obtain the porous silicon nano material of about 0.5 g yellowish-brown crystallization.The x-ray powder of the porous silicon nano material
Diffraction patterns are basically identical with Fig. 2.Nitrogen adsorption test result shows that the material specific surface area is 160 m2 g-1, display is substantially
Mesopore orbit（The nm of aperture about 2.9 and 28 nm）.The battery performance with reference to made from the step of embodiment 1 the 3rd and four-step method with
The effect of embodiment 1 is identical.
Embodiment 6
By 1.0 mL Tri-n-Propylamines and 1.0 mL SiCl4It is added in 40 mL N- methylimidazoles, is stirred at room temperature overnight.Add 1
g Mg2Si, it is placed in reactor and is reacted 48 hours at 200 DEG C.Centrifugation, chloroform 3 ~ 4 times, vacuum drying, obtain brown
Solid.
Obtained brown solid is placed on and is connected with the tube furnace of high-purity Ar gas, with 15 DEG C of min-1Heating rate
To 700 DEG C and kept for 30 minutes.After Temperature fall, obtained solid is washed with 1 M HCl, then with distillation water washing number
It is secondary, vacuum drying, obtain the porous silicon nano material of about 0.4 g yellowish-brown crystallization.The x-ray powder of the porous silicon nano material
Diffraction patterns are basically identical with Fig. 2.Nitrogen adsorption test result shows that the material specific surface area is 190 m2 g-1, display is substantially
Mesopore orbit（The nm of aperture about 3.3 and 26 nm）.The battery performance with reference to made from the step of embodiment 1 the 3rd and four-step method with
The effect of embodiment 1 is essentially identical.
Embodiment 7
By 1 mL N- methylimidazoles and 1.1 mL HSiCl3It is added in 40 mL dry toluenes, is stirred at room temperature overnight.Add 1
g Mg2Si, it is placed in reactor and is reacted 24 hours at 170 DEG C.Centrifugation, chloroform 3 ~ 4 times, vacuum drying, obtain brown
Solid.
Obtained brown solid is placed on and is connected with the tube furnace of high-purity Ar gas, with 15 DEG C of min-1Heating rate
To 700 DEG C and kept for 30 minutes.After Temperature fall, obtained solid is washed with 1 M HCl, then with distillation water washing number
It is secondary, vacuum drying, obtain the porous silicon nano material of about 0.4 g yellowish-brown crystallization.The x-ray powder of the porous silicon nano material
Diffraction patterns are basically identical with Fig. 2.Nitrogen adsorption test result shows that the material specific surface area is 230 m2 g-1, display is substantially
Mesopore orbit（The nm of aperture about 3.5 and 25 nm）.The battery performance with reference to made from the step of embodiment 1 the 3rd and four-step method with
The effect of embodiment 1 is essentially identical.
Embodiment 8
By 1 mL pyrroles and 1.1 mL HSiCl3It is added in 40 mL dry toluenes, is stirred at room temperature overnight.Add 1 g
Mg2Si, it is placed in reactor and is reacted 24 hours at 150 DEG C.Centrifugation, chloroform 3 ~ 4 times, vacuum drying, obtain brown and consolidate
Body.
Obtained brown solid is placed on and is connected with the tube furnace of high-purity Ar gas, with 15 DEG C of min-1Heating rate
To 700 DEG C and kept for 30 minutes.After Temperature fall, obtained solid is washed with 1 M HCl, then with distillation water washing number
It is secondary, vacuum drying, obtain the porous silicon nano material of about 0.4 g yellowish-brown crystallization.The x-ray powder of the porous silicon nano material
Diffraction patterns are basically identical with Fig. 2.Nitrogen adsorption test result shows that the material specific surface area is 210 m2 g-1, display is substantially
Mesopore orbit（The nm of aperture about 3.1 and 24 nm）.The battery performance with reference to made from the step of embodiment 1 the 3rd and four-step method with
The effect of embodiment 1 is essentially identical.
Embodiment 9
By 1 mL Tri-n-Propylamines and 2.0 mL HSiCl3It is added to the anhydrous CH of 40 mL2Cl2In, it is stirred at room temperature overnight.Add 1 g
Mg2Si, at room temperature stirring reaction 10 hours.Centrifugation, chloroform 3 ~ 4 times, vacuum drying, obtain brown solid.By what is obtained
Brown solid is directly washed with 1 M HCl, is dried to obtain the porous silicon nano material of 0.82 g yellowish-brown.The porous silicon nanometer material
The X-ray powder diffraction figure of material is shown as impalpable structure.Nitrogen adsorption test result shows that with aperture be 3.6 nm and 25
Nm mesopore orbit, specific surface area are 235 m2 g-1.The battery performance with reference to made from the step of embodiment 1 the 3rd and four-step method
It is essentially identical with the effect of embodiment 1.
Embodiment 10
By 1 mL Tri-n-Propylamines and 1.1 mL HSiCl3It is added to the anhydrous CH of 40 mL2Cl2In, it is stirred at room temperature overnight.Add 2 g
Cetyl trimethylammonium bromide（CTAB）With 1 g Mg2Si, at room temperature stirring reaction 24 hours.Chloroform washs, drying,
It is heat-treated 30 minutes under 700 DEG C of Ar atmosphere.1 M HCl are washed, and are washed, and drying, obtain about 0.5 g brown solids.Fig. 7 is
The N of the porous silicon2Adsorption desorption curve and graph of pore diameter distribution, from N2Adsorption desorption curve and pore size distribution curve can be seen that the material
Specific surface area is 450 m2 g-1, show regular mesopore orbit, the nm of aperture about 3.5.With reference to the step of embodiment 1 the 3rd and the 4th step
Battery performance made from method and the effect of embodiment 1 are essentially identical.
Embodiment 11
By 1 mL Tri-n-Propylamines and 1.1 mL HSiCl3It is added to the anhydrous CH of 40 mL2Cl2In, it is stirred at room temperature overnight.Add 1 g
DTAB and 1 g Mg2Si, at room temperature stirring reaction 24 hours.Chloroform washs, drying, 700 DEG C
It is heat-treated 30 minutes under Ar atmosphere.1 M HCl are washed, and are washed, and drying, obtain about 0.5 g brown solids.Nitrogen adsorption is tested
As a result it is 410 m to show the material specific surface area2 g-1, show regular mesopore orbit, the nm of aperture about 3.0.With reference to embodiment 1
Battery performance and the effect of embodiment 1 are essentially identical made from 3rd step and four-step method.
Embodiment 12
By porous silicon nano material and dopamine in mass ratio 1 made from the second step of embodiment 1:1 is blended in 100 mL buffering
In solution, it is stirred at room temperature 24 hours, filters, with distillation water washing three times, vacuum drying.Under an ar atmosphere with 2 DEG C/min liter
Warm speed is warming up to 400 DEG C and kept for 2 hours, is then warming up to 800 DEG C with 5 DEG C/min heating rate and is kept for 3 hours
To carbon coating porous silicon composite material.The battery performance with reference to made from the four-step method of embodiment 1 is identical with the effect of embodiment 1.
Embodiment 13
Porous silicon nano material made from the second step of embodiment 1 is dispersed in dissolved with a certain amount of (in mass ratio 2:1) glucose
In ethanol, 200 DEG C of hydro-thermal process 5 hours, filtering, washing, drying.Or by porous silicon nano material ultrasonic disperse dissolved with certain
Amount (in mass ratio 2:1) in the water of sucrose, solid is obtained by Rotary drying after stirring 4 hours.The solid that both obtain is lazy
Property atmosphere it is lower 700 DEG C be heat-treated 3 hours.Battery performance and the effect phase of embodiment 1 with reference to made from the four-step method of embodiment 1
Together.
It should be appreciated that for those of ordinary skills, can according to the above description be improved or converted,
And all these modifications and variations should all belong to the protection domain of appended claims of the present invention.
Claims (8)
- A kind of 1. preparation method of porous silicon nano material, it is characterised in that by chlorosilane under activator effect, room temperature to 200 At DEG C in anhydrous organic solvent with after silication reactive magnesium, reaction product passes through water or acid solution wash, is dried to obtain amorphous Porous silicon nano material, the activator be ammonia, organic amine, pyroles, pyridines, one kind in imidazoles material or several Kind.
- 2. the preparation method of porous silicon nano material as claimed in claim 1, it is characterised in that the chlorosilane is SiCl4, HSiCl3Or Si2Cl6In one or more.
- 3. the preparation method of porous silicon nano material as claimed in claim 1, it is characterised in that the activator is NH3, pyrrole Cough up, pyridine, N- methylimidazoles, triethylamine, Tri-n-Propylamine, tri-n-butylamine, the one or more in dibutyl amine or butylamine.
- 4. the preparation method of porous silicon nano material as claimed in claim 1, it is characterised in that by adding in reaction system Add surfactant, be made and lived with the mesoporous porous silicon nano material of rule, the surfactant for chain alkyl surface Property agent.
- 5. the preparation method of porous silicon nano material as claimed in claim 4, it is characterised in that the surfactant is ten One or more in eight alkyl trimethyl ammonium bromides, cetyl trimethylammonium bromide, DTAB.
- 6. the preparation method of the porous silicon nano material as described in claim 1-5, it is characterised in that further will be unbodied Porous silicon nano material high temperature Crystallizing treatment, or by after the first high temperature Crystallizing treatment under an ar atmosphere of reaction product under an ar atmosphere Pass through water or acid solution wash, drying, the porous silicon nano material crystallized again.
- 7. a kind of porous silicon nano material, it is characterised in that be prepared using such as any one of claim 1-6 methods described, be Porous silica material with mesopore orbit.
- 8. the porous silicon nano material described in claim 7 is preparing lithium ion battery negative material or is being used as molecular sieve material Material, the application in absorption, separation, catalysis, medical field.
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| CN113237969A (en) * | 2021-04-21 | 2021-08-10 | 南京大学 | Preparation of monodisperse mesoporous silicon nano chromatographic packing with center-through and radial aperture and application of packing in chromatographic separation |
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