CN103626187B - A kind of preparation method of height ratio capacity porous silicon oxide compound - Google Patents
A kind of preparation method of height ratio capacity porous silicon oxide compound Download PDFInfo
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- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 43
- -1 silicon oxide compound Chemical class 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims abstract description 63
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 18
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- 238000005260 corrosion Methods 0.000 claims abstract description 16
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
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- 230000001681 protective effect Effects 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 18
- 239000005543 nano-size silicon particle Substances 0.000 abstract description 14
- 238000007323 disproportionation reaction Methods 0.000 abstract description 11
- 239000000377 silicon dioxide Substances 0.000 abstract description 7
- 239000008151 electrolyte solution Substances 0.000 abstract description 3
- 239000008187 granular material Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
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- 229910052593 corundum Inorganic materials 0.000 description 8
- 239000010431 corundum Substances 0.000 description 8
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- 238000001035 drying Methods 0.000 description 7
- 239000002153 silicon-carbon composite material Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 230000003628 erosive effect Effects 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000004087 circulation Effects 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 239000002648 laminated material Substances 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
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- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
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- 238000011056 performance test Methods 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
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- 238000011065 in-situ storage Methods 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention belongs to field of lithium ion battery, particularly a kind of preparation method of height ratio capacity porous silicon oxide compound.The preparation method of this height ratio capacity porous silicon oxide compound, is raw material with silicon monoxide, it is characterized by, and by silicon monoxide under protective atmosphere or vacuum condition, processes 8-20h, cool to room temperature with the furnace at 900-1200 DEG C; Product is placed in plastic containers, adds hydrofluoric acid aqueous solution corrosion treatment, react under ultrasound condition; By reacting liquid filtering, with deionized water wash, product vacuum is dry, obtains product.Preparation method of the present invention is simple, only need to corrode two steps by pyroprocessing and hydrofluoric acid and just can obtain porous silicon oxide compound, the nano silicon particles that next silica portion disproportionation of high temperature generates can reduce Volumetric expansion, under ultrasound condition, hydrofluoric acid corrosion forms the porous silicon oxide compound of deep hole, is convenient to electrolytic solution and enters granule interior.
Description
(1) technical field
The invention belongs to field of lithium ion battery, particularly a kind of preparation method of height ratio capacity porous silicon oxide compound.
(2) background technology
The fast development of electromobile and smart mobile phone etc. is had higher requirement to lithium ion battery, business-like lithium ion battery negative adopts graphite, its theoretical specific capacity only has 372mAh/g, finds safety, height ratio capacity and can the negative material of fast charging and discharging be the emphasis of the focus paid close attention to of researcher and research all the time.During Lithium-ion embeding silicon, 1 Siliciumatom can be formed containing the very high alloy Li of lithium amount in conjunction with 4.4 lithium atoms at most
4.4si, its theoretical specific capacity is 4200mAh/g, exceedes more than 10 times, commercial Li-ion battery negative material graphite, is the negative material with extra best best specific storage known at present.Silicon is the element of content second in the earth's crust simultaneously, has rich in natural resources, so silica-base material is the negative material of new generation of most magnetism in the research of current lithium ion battery negative material.But in the process embedding lithium, the volumetric expansion of silicon, more than 300%, makes silicon materials breaking and Dusting in working cycle, lose with current collector and to contact and to cause the specific storage of whole negative material sharply to decline even almost nil.
In order to overcome the above problems, the compound that investigator proposes to adopt the less negative material of some volumetric expansions in charge and discharge process and silicon materials to be combined into the battery performance, particularly silicon and autoxidation thing that matrix material effectively can improve silicon does not only introduce other impurity but also be the key broken through by flexible and changeable forming.Silica has specific storage more than 1600mAh/g than the silicon monoxide for 1:1 as the negative material of lithium ion battery, but it exists the Study of Volume Expansion in charge and discharge process equally.The people such as Jung-InLee (Jung-InLee, KyuTaeLee, JaephilCho, JeyoungKim, Nam-SoonChoiandSoojinPark.Angew.Chem.Int.Ed.2012,51,2767) use argent in-situ corrosion silicon monoxide particle to prepare its battery performance of porous silicon monoxide particle to be significantly improved, but use expensive Silver Nitrate to make there is no actual productive value.Chinese patent CN102491335A discloses " a kind of preparation method of silicon nanoparticle and the negative material containing this silicon nanoparticle and lithium ion battery ", adopts the high temperature disproportionation reaction of silicon monoxide and hydrofluoric acid erosion removal silicon-dioxide to prepare the negative material of silicon nanoparticle; Chinese patent CN102522534A discloses " a kind of high-specific-capacity silicon carbon matrix material and preparation method thereof, lithium ion battery negative material and lithium ion battery ", adopt silicon monoxide high temperature disproportionation, the negative material of porous carbon comprehensive silicon nanoparticle is prepared in hydrofluoric acid corrosion; Chinese patent CN102447112A discloses " a kind of Si-C composite material and preparation method thereof and containing the negative material of this Si-C composite material and lithium ion battery ", adopt silicon monoxide high temperature disproportionation, the negative material that porous carbon bag covers nano-silicon is prepared in hydrofluoric acid corrosion; Chinese patent CN102437318A discloses " a kind of preparation method of Si-C composite material, prepared Si-C composite material and the lithium ion battery negative containing this Si-C composite material and battery ", adopt the coated silicon monoxide of carbon, then prepare the Si-C composite material of nucleocapsid structure through thermal treatment and hydrofluoric acid corrosion.
Improve a lot although above patent corrodes by the high temperature disproportionation of silicon monoxide and hydrofluoric acid its cycle performance of Si-C composite material obtained, but the use due to a large amount of complex carbon material reduces overall specific storage, particularly corrode all silicon-dioxide and silicon monoxide with a large amount of hydrofluoric acid, not only waste silicon monoxide starting material and hydrofluoric acid, and make nano-silicon lack silicon oxide as volumetric expansion buffer reagent, thus causing specific storage lower, efficiency is lower first.
(3) summary of the invention
The present invention, in order to make up the deficiencies in the prior art, provides the preparation method of the height ratio capacity porous silicon oxide compound that a kind of preparation method is simple, cost is lower, be produced on a large scale.
The present invention is achieved through the following technical solutions:
A preparation method for height ratio capacity porous silicon oxide compound, take silicon monoxide as raw material, comprises the steps:
(1) by silicon monoxide under protective atmosphere or vacuum condition, 8-20h is processed at 900-1200 DEG C, cool to room temperature with the furnace, the silicon monoxide meeting generating portion disproportionation of pyroprocessing, generate nano silicon particles and silicon-dioxide, nano level silicon grain can reduce Volumetric expansion, strengthens cycle performance;
(2) product of step (1) is placed in plastic containers, adds hydrofluoric acid aqueous solution corrosion treatment, react under ultrasound condition;
(3) by the reacting liquid filtering of step (2), with deionized water wash, product vacuum is dry, obtains product.
More excellent scheme of the present invention is:
Described silicon monoxide is micron particle, and granular size is 325 orders, is mostly point cantact in electrode between particle, therefore small-particle resistance is comparatively large, and large specific surface area forms a large amount of solid electrolyte membranes simultaneously, reduces gram volume; Macrobead can affect the processing characteristics of coating quality and pole piece, and 325 object granularities are sizes of over-all properties optimum.
In step (1), protective atmosphere is nitrogen, argon gas, nitrogen hydrogen mixed gas or argon gas hydrogen mixed gas, and preferred gas is high-purity gas, and wherein in mixing tank, the volume ratio of hydrogen is 10%.
In step (1), vacuum condition is that pressure is less than 10Pa, and preferably pressure is less than 1 × 10
-2pa, pressure is lower, and fewer silicon monoxide is oxidized, and its specific storage is higher.
In step (2), add the hydrofluoric acid aqueous solution corrosion treatment that mass concentration is 10-40% in plastic containers, the mol ratio of hydrofluoric acid and silicon monoxide is 1-2:1, reacts 15-120min under ultrasound condition; Silicon-dioxide and the corrosion of part silicon monoxide are formed the silicon oxide compound of porous by hydrofluoric acid; Under ultrasound condition, stronger to the etch selectivities of particle, more easily form the porous silicon oxide compound of deep hole, be convenient to electrolytic solution and enter the diffusion of granule interior enhancing lithium ion, hold the volumetric expansion in charge and discharge process; Within 15 minutes, most of particle erosion can be generated the silicon oxide compound of porous, although the porous silicon oxide compound generated can swim in above reaction solution and no longer be corroded by hydrofluoric acid under ultrasonic condition, but the porous silicon oxide compound activity generated is higher, so the reaction times controlled within 2 hours.
In step (3), vacuum drying temperature is 80-120 DEG C, and the time is 2-20h, and under vacuum condition, drying to ensure that in drying process, porous silicon oxide compound is not by the dioxygen oxidation in air, and dry object removes water.
The present invention has prepared porous silicon oxide compound by pyroprocessing and ultrasonic lower hydrofluoric acid corrosion, and the porous silicon oxide polymer beads of preparation is evenly distributed, and the battery specific storage of assembling is high, and cycle performance is excellent.
Preparation method of the present invention is simple, only need to corrode two steps by pyroprocessing and hydrofluoric acid and just can obtain porous silicon oxide compound, the nano silicon particles that next silica portion disproportionation of high temperature generates can reduce Volumetric expansion, under ultrasound condition, hydrofluoric acid corrosion forms the porous silicon oxide compound of deep hole, is convenient to electrolytic solution and enters granule interior.Whole production process does not have complicated equipment and processing step is simple, is convenient to large-scale industrial production and the stability of product is better, and energy consumption is lower.This porous silicon oxide compound has the structure of nano silicon particles and porous, the volumetric expansion in charge and discharge process can be held and be conducive to the deintercalation of lithium ion, therefore this porous silicon oxide compound has high specific storage, stable cycle performance, contrasting common silicon monoxide particle has obvious progress.By battery prepared by the present invention, first discharge specific capacity reaches 1453mAh/g, and the conservation rate of 50 times is more than 75%.
(4) accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is further illustrated.
Fig. 1 is the discharge cycles performance test figure of the lithium ion battery that the porous silicon oxide laminate material of the embodiment of the present invention 1 preparation is made.
Fig. 2 is the discharge cycles performance test figure of the lithium ion battery that the porous silicon oxide laminate material of the embodiment of the present invention 2 preparation is made.
Fig. 3 is the lithium ion battery made of porous silicon oxide laminate material prepared of the embodiment of the present invention 3 at the charging and discharging curve of the 1st, 2,25,50 time.
Fig. 4 is the lithium ion battery made of porous silicon oxide laminate material prepared of the embodiment of the present invention 4 at the charging and discharging curve of the 1st, 30,50 time.
(5) embodiment
Below by specific embodiments, the present invention is described in further detail, but these embodiments are only to illustrate, do not limit scope of the present invention.
Embodiment 1:
4.4g silicon monoxide particle is put into corundum Noah's ark, and tube furnace put into by corundum Noah's ark, opens mechanical pump, after being evacuated to 5Pa, opening molecular pump, is evacuated to 10
-2pa.Be warming up to 1000 DEG C with 10 DEG C of per minutes, be incubated 8 hours, cool to room temperature with the furnace, part silicon monoxide generation disproportionation generates nano silicon particles in the process.
The product of preparation is placed in plastic beaker, add the hydrofluoric acid aqueous solution that 40ml massfraction is 10%, stir after 10 minutes, ultrasonic erosion 2 hours, in corrosion process, the porous silicon oxide compound generated swims in above reaction solution and is no longer corroded by hydrofluoric acid, and along with the prolongation of etching time, more porous silicon oxide compound swims in above reaction solution.Reaction terminates rear filtration, deionized water wash three times, and in vacuum drying oven, 120 DEG C of dryings obtain porous silicon oxide compound in 2 hours.
By the porous silicon oxide compound of gained and conductive agent acetylene black, binding agent PVDF(polyvinylidene difluoride (PVDF)) in mass ratio 80:10:10 mix, add NMP(1-methyl-2 pyrrolidone) mixture is modulated into slurry, evenly be coated on Copper Foil, 80 DEG C of dryings 6 hours, 120 DEG C of vacuum-drying, 12 hours obtained pole pieces, pole piece is transferred in glove box, with metallic lithium for be assembled into CR2032 type button cell to pole.
By the battery of this case making, first discharge specific capacity reaches 1110mAh/g, still has 762mAh/g after 41 circulations.
Embodiment 2:
4.4g silicon monoxide particle is put into corundum Noah's ark, and tube furnace put into by corundum Noah's ark, with 100sccm(standard-statecubiccentimeterperminute, mark condition milliliter per minute) flow velocity pass into nitrogen after 2 hours.Be warming up to 900 DEG C with 10 DEG C of per minutes, be incubated 20 hours, cool to room temperature with the furnace, part silicon monoxide generation disproportionation generates nano silicon particles in the process.
The product of preparation is placed in plastic beaker, add the hydrofluoric acid aqueous solution that 15ml massfraction is 20%, stir after 10 minutes, ultrasonic erosion 15 minutes, in corrosion process, the porous silicon oxide compound generated swims in above reaction solution and is no longer corroded by hydrofluoric acid, and along with the prolongation of etching time, more porous silicon oxide compound swims in above reaction solution.Reaction terminates rear filtration, deionized water wash three times, and in vacuum drying oven, 80 DEG C of dryings obtain porous silicon oxide compound in 20 hours.
The making method of button cell is as embodiment 1, and by the battery of this case making, first discharge specific capacity reaches 862mAh/g, has 937mAh/g after 50 circulations.
Embodiment 3:
4.4g silicon monoxide particle is put into corundum Noah's ark, and tube furnace put into by corundum Noah's ark, passes into argon gas hydrogen mixed gas with the flow velocity of 100sccm, and hydrogen ratio is 10%.After 2 hours, be warming up to 1200 DEG C with 10 DEG C of per minutes, be incubated 12 hours, cool to room temperature with the furnace, part silicon monoxide generation disproportionation generates nano silicon particles in the process.
The product of preparation is placed in plastic beaker, add the hydrofluoric acid aqueous solution that 10ml massfraction is 40%, stir after 10 minutes, ultrasonic erosion 1 hour, in corrosion process, the porous silicon oxide compound generated swims in above reaction solution and is no longer corroded by hydrofluoric acid, and along with the prolongation of etching time, more porous silicon oxide compound swims in above reaction solution.Reaction terminates rear filtration, deionized water wash three times, and in vacuum drying oven, 80 DEG C of dryings obtain porous silicon oxide compound in 8 hours.
The making method of button cell is as embodiment 1, and by the battery of this case making, first discharge specific capacity reaches 1453mAh/g, still has 1097mAh/g after 50 circulations.
Embodiment 4:
4.4g silicon monoxide particle is put into corundum Noah's ark, and tube furnace put into by corundum Noah's ark, opens mechanical pump, is evacuated to 10Pa.Be warming up to 1100 DEG C with 10 DEG C of per minutes, be incubated 12 hours, cool to room temperature with the furnace, part silicon monoxide generation disproportionation generates nano silicon particles in the process.
The product of preparation is placed in plastic beaker, add the hydrofluoric acid aqueous solution that 20ml massfraction is 10%, stir after 10 minutes, ultrasonic erosion 30 minutes, in corrosion process, the porous silicon oxide compound generated swims in above reaction solution and is no longer corroded by hydrofluoric acid, and along with the prolongation of etching time, more porous silicon oxide compound swims in above reaction solution.Reaction terminates rear filtration, deionized water wash three times, and in vacuum drying oven, 100 DEG C of dryings obtain porous silicon oxide compound in 12 hours.
The making method of button cell is as embodiment 1, and by the battery of this case making, first discharge specific capacity reaches 902mAh/g, still has 866mAh/g after 50 circulations.
Claims (6)
1. a preparation method for height ratio capacity porous silicon oxide compound, is raw material with silicon monoxide, it is characterized by, and comprises the steps: (1) by silicon monoxide under protective atmosphere or vacuum condition, processes 8-20h, cool to room temperature with the furnace at 900-1200 DEG C; (2) product of step (1) is placed in plastic containers, the hydrofluoric acid aqueous solution corrosion treatment that mass concentration is 10-40% is added in plastic containers, the mol ratio of hydrofluoric acid and silicon monoxide is 1-2:1,15-120min(3 is reacted under ultrasound condition) by the reacting liquid filtering of step (2), with deionized water wash, product is vacuum-drying 2-20h at 80-120 DEG C, obtains product.
2. the preparation method of height ratio capacity porous silicon oxide compound according to claim 1, it is characterized in that: described silicon monoxide is micron particle, granular size is 325 orders.
3. the preparation method of height ratio capacity porous silicon oxide compound according to claim 1, is characterized in that: in step (1), protective atmosphere is nitrogen, argon gas, nitrogen hydrogen mixed gas or argon gas hydrogen mixed gas.
4. the preparation method of height ratio capacity porous silicon oxide compound according to claim 1, is characterized in that: in step (1), vacuum condition is that pressure is less than 10Pa.
5. the preparation method of height ratio capacity porous silicon oxide compound according to claim 3, is characterized in that: in step (1), the gas of protective atmosphere is high-purity gas, and wherein in gas mixture, the volume ratio of hydrogen is 10%.
6. the preparation method of height ratio capacity porous silicon oxide compound according to claim 4, is characterized in that: in step (1), vacuum condition is that pressure is less than 1 × 10
-2pa.
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| CN106654228A (en) * | 2017-01-20 | 2017-05-10 | 中天储能科技有限公司 | Preparation method of porous SiOx core-shell microspheres |
| CN106848264A (en) * | 2017-04-01 | 2017-06-13 | 江苏中天科技股份有限公司 | A kind of porous silicon oxide lithium ion battery negative material and preparation method thereof |
| CN110783531A (en) * | 2018-07-31 | 2020-02-11 | 纳米及先进材料研发院有限公司 | Method for preparing electrode active material and battery electrode |
| CN109384231A (en) * | 2018-11-07 | 2019-02-26 | 苏州宇量电池有限公司 | A kind of preparation method of nano silicon material |
| CN110085853A (en) * | 2019-05-30 | 2019-08-02 | 郑州中科新兴产业技术研究院 | Aoxidize sub- silicon substrate carbon negative pole material, cathode pole piece and preparation method thereof and lithium ion battery |
| CN113517422A (en) * | 2021-04-02 | 2021-10-19 | 江西紫宸科技有限公司 | Carbon-coated porous silicon oxide material and preparation method and application thereof |
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| CN102491335A (en) * | 2011-11-30 | 2012-06-13 | 奇瑞汽车股份有限公司 | Method for preparing silicon nanoparticles, anode material containing silicon nanoparticles, and lithium ion battery |
| CN102522534A (en) * | 2012-01-09 | 2012-06-27 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material with high specific capacity, preparation method of silicon-carbon composite material, lithium ion battery anode material and lithium ion battery |
| CN103236517A (en) * | 2013-04-26 | 2013-08-07 | 中国东方电气集团有限公司 | Lithium ion battery silicon-based negative material and preparation method thereof |
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