CN106684364A - Nano porous material and preparation method thereof - Google Patents
Nano porous material and preparation method thereof Download PDFInfo
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- CN106684364A CN106684364A CN201710056842.2A CN201710056842A CN106684364A CN 106684364 A CN106684364 A CN 106684364A CN 201710056842 A CN201710056842 A CN 201710056842A CN 106684364 A CN106684364 A CN 106684364A
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- porous material
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000007783 nanoporous material Substances 0.000 title abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 24
- 239000007772 electrode material Substances 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims description 93
- 238000000498 ball milling Methods 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 33
- 239000012298 atmosphere Substances 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 24
- 229910001416 lithium ion Inorganic materials 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 20
- 238000005554 pickling Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000008246 gaseous mixture Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- 238000001069 Raman spectroscopy Methods 0.000 claims description 3
- 239000002322 conducting polymer Substances 0.000 claims description 3
- 229920001940 conductive polymer Polymers 0.000 claims description 3
- 239000002178 crystalline material Substances 0.000 claims description 3
- 125000003184 C60 fullerene group Chemical group 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000008188 pellet Substances 0.000 claims description 2
- 229910021384 soft carbon Inorganic materials 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 claims 1
- 239000013067 intermediate product Substances 0.000 description 23
- 239000000047 product Substances 0.000 description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229910008062 Si-SiO2 Inorganic materials 0.000 description 5
- 229910006403 Si—SiO2 Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000008187 granular material Substances 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910021426 porous silicon Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000011863 silicon-based powder Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a nano porous material and a preparation method thereof. The nano porous material contains an M elementary substance, wherein M is Si and/or Ge; the nano porous material has a grain size of 20-150 nm, a porosity of 0.2-0.8 and a specific surface area of 15-300 m<2>/g. As an electrode material, the nano porous material has better performance.
Description
Technical field
The invention belongs to field of nanometer material technology, and in particular to nano-porous materials and preparation method thereof.
Background technology
Lithium ion battery has the advantages that specific energy height, small volume, lightweight, cycle life is high, self discharge is little, portable
The fields such as formula electronic equipment, electric automobile, space technology, national defense industry are all widely used.
In many energy-density lithium ion battery negative materials of new generation, silicon has high (the about graphite of theoretical capacity
13 times), abundance the advantages of, be following to replace one of material of most rich potentiality of graphite cathode material.However, silicon is in charge and discharge
Huge volumetric expansion can occur in electric process, cause battery capacity rapid attenuation.By silicon materials nanorize, for example, prepare silicon and receive
Rice grain, silicon nanowires etc., are one of approach for solving the above problems.
The content of the invention
It is an object of the present invention to provide a kind of porous material, it is also another object of the present invention to provide a kind of porous material
The preparation method of material, it is also another object of the present invention to provide a kind of compositionss, further object of the present invention is to provide above-mentioned group
The preparation method of compound, further object of the present invention is to provide a kind of lithium ion battery.
One aspect of the present invention provides a kind of porous material, and it contains M simple substance, and M is Si and/or Ge；
The granularity of the porous material is 20~150nm, and porosity is 0.2~0.8, and specific surface area is 15~300m2/g。
In one embodiment, the porous material of any one of the present invention, it has following one or more feature,
Preferably, the granularity of the porous material be 50~150nm, such as such as 50~130nm, 50~110nm, such as 60
~100nm, then such as 70~90nm；
Preferably, the porosity of the porous material is 0.3~0.8, such as 0.4~0.8, such as 0.5~0.8, such as 0.6
~0.7；
Preferably, the specific surface area of the porous material is 40~300m2/ g, then such as 100~300m2/ g, then such as 150
~300m2/ g, then such as 200~300m2/ g, then such as 230~300m2/ g, then such as 230~270m2/ g, then such as 240~
260m2/g；
Preferably, the apparent density of the porous material is 0.5~2.2g/cm3, such as 0.5~2g/cm3, such as 0.5~
1.5g/cm3, such as 0.6~1.1g/cm3, such as 0.6~0.8g/cm3；
Preferably, the pore size distribution curve of the porous material has characteristic peak in 10~50nm, for example, have feature in 5~15nm
Peak, then for example have characteristic peak in 15~25nm, then for example have characteristic peak in 25~35nm；
Preferably, only one of which characteristic peak on the pore size distribution curve of the porous material；
Preferably, in the TEM photos of the 40 of the porous material~500,000 times, it is able to observe that loose structure (such as cystose
Loose structure)；
Preferably, the porous material contains M simple substance more than 50 weight %；
Preferably, the porous material contains M simple substance more than 90 weight %；
Preferably, the porous material contains M simple substance more than 99 weight %；
Preferably, M is Si.
Another aspect of the invention provides a kind of method for preparing porous material, and it includes：
I) ball milling raw material M simple substance and the mixture of oxidant, obtain the oxide of M；
M is Si and/or Ge；
Ii) the oxide of heat treatment M；
Iii) the oxide of the M after pickling heat treatment；
Preferably, the porous material is the porous material of any one of the present invention.
In one embodiment, the method for any one of the present invention, step i) has following one or more feature：
Preferably, the purity of raw material M simple substance is greater than about 99.5%, preferably greater than 99.9%；
Preferably, raw material M simple substance to be shaped as spherical, near-spherical, bulk, class block, bar-shaped or irregularly shaped；
Preferably, the volume of raw material M simple substance is 1~10mm3, preferably 3~7mm3；
Preferably, raw material M simple substance and the mol ratio of the oxidant are 1:0.8~1.8, such as 1:1.0~1.5, then example
Such as 1:1.2~1.4.
In one embodiment, the method for any one of the present invention, step i) has following one or more feature：
Preferably, the oxidant includes water；
Preferably, ball milling is carried out under vacuum or nonoxidizing atmosphere, and nonoxidizing atmosphere can be inert gas atmosphere, for example
Argon atmospher；
Preferably, the rotating speed of ball milling is 500~2000r/min, such as 800~1200r/min；
Preferably, the ball radius that ball milling is used are 1~5mm, such as 3~4mm；
Preferably, the material of the abrading-ball that ball milling is used is ZrO2；
Preferably, the pellet mass ratio of ball milling is 1:20；
Preferably, the time of ball milling is 1~5 hour, such as 3~4 hours.
In one embodiment, the method for any one of the present invention, step i) has following one or more feature：
Preferably, the oxide of the M is MOx, x=0.2~1.8 (such as x=0.5~1.7, such as x=1.0~
1.6, then such as x=1.2~1.4)；
Preferably, the oxide of the M is non-crystalline material；
Preferably, the oxide of the M is that granularity is 50~200nm, such as 50~150nm.
Preferably, in the TEM photos of the oxide of the M, without obvious crystal structure；
Preferably, it is have steamed bun peak in the range of 10~40 ° at 2 θ angles in the XRD curves of the oxide of the M；
Preferably, the oxide of the M is with the XRD curves shown in the curve b such as Fig. 2；
Preferably, the oxide of the M is in Raman spectrogram, in 475~500cm of wavelength-1Position have peak.
In one embodiment, the method for any one of the present invention, step ii) there is following one or more feature：
Preferably, heat treatment is carried out under vacuum or nonoxidizing atmosphere, and nonoxidizing atmosphere is, for example, inert gas atmosphere, example
The gaseous mixture atmosphere of argon and hydrogen in this way, the content of hydrogen is 1~3 volume % in preferred nonoxidizing atmosphere；
Preferably, the temperature of heat treatment is 500~1500 DEG C, e.g. 800~1200 DEG C；
Preferably, the time of heat treatment is 1~5 hour, such as 3~5 hours.
In one embodiment, the method for any one of the present invention, step iii) there is following one or more feature：
Preferably, the acid that pickling is used includes Fluohydric acid., and the concentration of Fluohydric acid. is preferably 0.1~1mol/L, further preferably for
0.3~0.8mol/L；
Preferably, the time of pickling is more than 0.1 hour, preferably 0.3~0.7 hour；
Preferably, the one or multi-step in being filtered, washed and dried also is included after pickling.
Another aspect of the invention provides a kind of compositionss, the porous material containing conductive compositions He any one of the present invention；
Preferably, the conductive compositions are carbon and/or conducting polymer；
Preferably, the carbon is selected from graphite, hard carbon, soft carbon, white carbon black, activated carbon, C60, Graphene, graphene oxide or receive
One or more in rice carbon pipe；
Preferably, the compositionss are the porous material of any one of the present invention and the product of conductive compositions ball milling mixing.
In one embodiment, the compositionss of any one of the present invention, it has following one or more feature：
Preferably, the compositionss specific surface area is 2~30m2/ g, such as 5~30m2/ g, then such as 10~30m2/ g, then
Such as 15~30m2/ g, then such as 20~30m2/g；
Preferably, in the compositionss, M element is respectively 1 with the mass ratio of carbon:0.01~10, such as 1:0.1~
0.2；
Preferably, the compositionss are used as lithium ion battery negative material, under 1C electric current densities, after circulation 1000 weeks
Specific discharge capacity is 1000~1500mAh/g, such as 1100~1400mAh/g, then such as 1200~1300mAh/g.
Another aspect of the invention provides the preparation method of the compositionss of any one of the present invention, and it is comprised the following steps：
Ball milling after the porous material of any one of the present invention is mixed with the conductive compositions.
In one embodiment, the preparation method of any one compositionss of the present invention, its have following one or more it is special
Levy：
Preferably, ball milling is carried out under vacuum or nonoxidizing atmosphere, and nonoxidizing atmosphere can be inert gas atmosphere, for example
Argon atmospher；
Preferably, the rotating speed of ball milling is 300~800r/min, such as 500r/min；
Preferably, the time of ball milling is 1~3 hour, such as 2 hours；
Preferably, ball radius are 3~8mm, such as 5mm；
Preferably, the material of abrading-ball is ZrO2；
Preferably, raw material Si or raw material Ge and the mass ratio of abrading-ball are 1:15~25, such as 1:20.
In one embodiment, the porous material of any one of the present invention, or the compositionss of any one of the present invention are used as electricity
The purposes of pole material；
Preferably, the electrode material is lithium ion battery negative material.
Another aspect of the invention provides a kind of electrode material, it include the porous material described in any one of the present invention or
Compositionss described in any one of the present invention；
Preferably, the electrode material is lithium ion battery negative material.
Another aspect of the invention provides a kind of battery, and it includes the porous material of any one of the present invention or any one of the present invention
Compositionss；
Preferably, the negative material of the battery includes the porous material of any one of the present invention or the group of any one of the present invention
Compound；
Preferably, the battery is lithium ion battery.
In one embodiment, granularity be laser particle size diffractometer measurement mean diameter, such as laser particle size diffraction
Mean diameter D [2,0] of instrument measurement.
Beneficial effects of the present invention
One or more embodiments of the invention have following one or more advantage：
1) granularity of porous material is less；
2) porosity of porous material is higher；
3) specific surface area of porous material is larger；
4) pore volume of porous material is larger；
5) porous material or compositionss are higher as the specific capacity of lithium ion battery negative material；
6) porous material or compositionss are preferable as the cycle performance of lithium ion battery negative material；
7) process is simple of the preparation method of porous material；
8) low cost of the preparation method of porous material.
Description of the drawings
Accompanying drawing described herein is used for providing a further understanding of the present invention, constitutes the part of the application, this
Bright schematic description and description does not constitute limitation of the invention for explaining the present invention.In the accompanying drawings：
Fig. 1 is the Raman spectrogram of intermediate product A4 and A '；
Fig. 2 is X-ray diffraction (XRD) curve of intermediate product A4 and A '；
Fig. 3 is transmission electron microscope (TEM) photo of intermediate product A4；
Fig. 4 is transmission electron microscope (TEM) photo of intermediate product B4；
Fig. 5 is transmission electron microscope (TEM) photo of porous material D4；
Fig. 6 is the nitrogen adsorption-desorption curve of porous material D3~D5 and product D '；
Fig. 7 is the graph of pore diameter distribution of porous material D3~D5 and product D '；
Fig. 8 is transmission electron microscope (TEM) photo of porous material D4~D5；
Fig. 9 is the cycle performance curve of the lithium ion battery of embodiment 3.
Specific embodiment
Below by drawings and Examples, technical scheme is described in further detail.
Instrument and material used in embodiment is as shown in table 1 below：
Table 1
Embodiment 1~6
I) raw material Si simple substance and water (deionized water) are pressed into mixed in molar ratio shown in table 1, then ball milling.Raw material Si simple substance
For the Si blocks of purity about 99.9%, volume is for about 5mm3。
The atmosphere of ball milling is argon, and the rotating speed of ball mill is 1000r/min, and ball radius used by ball mill are 3mm, material
For ZrO2, the material ball ratio (gross mass of raw material elementary silicon and water:The quality of abrading-ball) it is 1:20, Ball-milling Time 3 hours obtains middle
Product A, numbering is A1~A6.
Ii) by the intermediate product A1 of step i)~A6 heat treatments in tube furnace.Heat treatment temperature is 1000 DEG C, and the time is
4 hours.Heat-treating atmosphere is argon hydrogen gaseous mixture (hydrogen accounts for 2 volumes %), and argon hydrogen mixed gas flow is 100sccm.In the middle of obtaining
Product B, numbering is B1~B6.
Iii) to step ii) intermediate product B1~B6 carry out pickling.Acid used by pickling is water-soluble for the Fluohydric acid. of 0.5M
Liquid, pickling time is 0.5 hour.Product Jing is filtered after pickling, wash and is dried, and obtain the porous material of embodiment 1~6
Material, numbering is D1~D6.
Comparative example 1
I) with reference to embodiment 1, raw material Si is individually carried out into ball milling in ball mill, without water.Raw material Si be purity about
99.9% Si blocks, volume is for about 5mm3。
The atmosphere of ball milling is argon.The rotating speed of ball mill is 1000r/min.Ball radius used by ball mill are 3mm.Ball milling
3 hours time, intermediate product A '.
Ii) by the intermediate product A ' of step i) in tube furnace heat treatment.Heat treatment temperature is 1000 DEG C, and the time is 4 little
When.Heat-treating atmosphere is argon hydrogen gaseous mixture (hydrogen accounts for 2 volumes %), and argon hydrogen mixed gas flow is 100sccm, obtains intermediate product
B’。
Iii) to step ii) intermediate product B ' carry out pickling.Acid used by pickling is Fluohydric acid., and Fluohydric acid. is 0.5M's
Hydrofluoric acid aqueous solution.Pickling time is 0.5 hour.Product Jing is filtered after pickling, wash and is dried, obtain the product of comparative example 1
Thing, numbering D '.
Table 1
Test and sign
(1) Fig. 1 illustrates the Raman spectrum collection of intermediate product A4 and A '.The curve A4 and A ' of Fig. 1 is produced in the middle of representing respectively
The Raman spectrum spectral line of thing A4 and A '.Curve A4 is shown in 475~500cm of wavelength-1Place's characteristic peak, illustrates that intermediate product A4 is
The oxide of Si, i.e. SiOxMaterial.Curve A ' is shown in 500~525cm of wavelength-1Place's characteristic peak, illustrates intermediate product A ' then
It is Si simple substance.
(2) Fig. 2 illustrates X-ray diffraction (XRD) collection of illustrative plates of intermediate product A4 and A '.During the curve A4 and A ' of Fig. 2 is respectively
Between product A4 and A ' XRD diffraction curves.Curve A4 has the distinctive steamed bun peak of amorphous in the position at 10~40 ° of 2 θ angles, illustrates A4
For non-crystalline material.Curve A ' shows diffraction maximums of the simple substance Si in [111], [220], [311], [400] and [331] crystal face, this
Illustrate that intermediate product A ' is elementary silicon.
(3) Fig. 3 illustrates transmission electron microscope (TEM) photo of intermediate product A4.As illustrated, the particle diameter of A4 is for about 50
~150nm, does not observe crystal structure in figure.The illustration in Fig. 3 upper right corner for intermediate product A4 electronogram, can be with figure
It was observed that dizzy shape diffraction pattern, further proves that intermediate product A4 is amorphous (amorphous) material.
(4) oxygen content of the intermediate product A1~A6 of embodiment 1~6 is analyzed using X-ray fluorescence spectra (XRF), is counted
SiO is calculatedxX values；The mean diameter (D [2,0]) of intermediate product A1~A6 and A ' is also have detected using laser particle size analyzer,
As a result it is as shown in table 2 below.
Table 2
(5) Fig. 4 is transmission electron microscope (TEM) photo of the intermediate product B4 of embodiment 4.As shown in figure 4, having in figure
The shallower granule of the color of multiple sizes about 50~150nm, is dispersed with the deeper region of multiple colors in these granules.Fig. 4 pieces
The illustration in the upper right corner is the electronogram of darker regions, and electronogram is ring-type, and according to electronogram these depths are judged
Zone domain is Si, thus the shallower granule of color just represents SiO in figure2.Figure explanation, intermediate product B4 contain Si simple substance and
SiO2, it is expressed as Si-SiO2Material.By step iii) pickling remove Si-SiO2SiO in material2Afterwards, that is, porous is obtained
Material.
(6) Fig. 5 for embodiment 4 porous material D4 transmission electron microscope (TEM) photo, amplification 40~500,000
Times.As shown in Figure 5, it can be observed that have the loose structure of cystose in figure, further prove that porous material D4 is porous.
(7) test of BET- nitrogen adsorptions has been carried out to the porous material D1~D6 of embodiment 1~6, their table has been measured
See density (g/cm3), actual porosity, specific surface area (m2/g)；Also with laser particle analyzer test porous material D1~
D6, and the mean diameter (nm) of the product D ' of comparative example 1.
Apparent density=sample quality/population of samples product；
Actual porosity=pore volume/population of samples product；
In addition, also calculating the theoretic porosity of porous material D1~D6, theoretic porosity is intermediate product B (Si-SiO2
Material) in SiO2Volume ratio of the total volume, i.e.,
Theoretic porosity=Si-SiO2SiO in material2Volume ÷ Si-SiO2All materials are accumulated.
Above test result is as shown in table 3 below.
Table 3
As shown in Table 3, the apparent density of porous material D1~D6 is 0.71~2.185g/cm3；Theoretic porosity is 0.25
~0.98；Actual porosity is 0.21~0.70；Mean diameter is 24~156nm.The mean diameter of product D ' is 177nm.
Fig. 6 illustrates the nitrogen adsorption-desorption curve of the product D ' of porous material D3~D5 and comparative example 1.
Fig. 7 illustrates the graph of pore diameter distribution of porous material D3~D5 and product D ', and abscissa is aperture (nm), and vertical coordinate is
dV/dlogD(cm3/g).Curve D3, D4, D5, D of Fig. 7 ' corresponds to respectively the pore-size distribution of porous material D3~D5 and product D '
Curve.The corresponding pore diameter range of pore size distribution curve peak value of D4 is in 5~15nm, the corresponding hole of pore size distribution curve peak value of D3
Footpath 15~25nm of scope, the corresponding 25~35nm of pore diameter range of peak value of the pore size distribution curve of D5.The pore size distribution curve of D '
Substantially without peak value.
(a) and (b) of Fig. 8 is respectively transmission electron microscope (TEM) photo of porous material D4 and D5, such as (a) of Fig. 8
Shown, D4 has obviously loose structure.As shown in (b) of Fig. 8, the minimum feature size of D5 is 5~10nm (minimal characteristics
Size refers to the size of the least unit of porous material inside silicon structure).
Embodiment 7~12
Ball milling is carried out after the porous material D1~D6 of embodiment 1 is mixed respectively with Graphene.Porous material and Graphene
Mass ratio be 10:1, the atmosphere of ball milling is argon, and the speed of ball milling is 500r/min, a diameter of 5mm of abrading-ball, and material ball ratio is
1:20, the time of ball milling is 2 hours.Obtain the compositionss of embodiment 7~12, numbering E1~E6.
The specific surface area of compositionss E1~E6 is measured with BET method, it is as shown in table 4 below.
Table 4
Comparative example 2
Using the metallic silicon of 98% purity as raw material, first clashed into the granule of millimeter magnitude (~10mm), then made
With ball mill, ball milling 5 hours under conditions of 500r/min.Product is entered into the AgNO of 20mM3In the HF solution of 5M, solvent
Using ethanol, react 2 hours at 50 DEG C.Finally the Ag on surface is removed within 1 hour using the nitric acid acidwashing sample of high concentration, obtained
Porous silicon powder, numbering is D ".
The porous silicon powder D that will be prepared " adds graphene oxide solution (Si:GO=1:1, mass ratio), ultrasound 1 hour,
And its surface of sucking filtration to mm pore size, it is dried in 110 DEG C of vacuum drying ovens, then sample is cut into into strip, in tubular type
In argon hydrogen gaseous mixture (volume % of hydrogen content 2) atmosphere in stove, anneal 1 hour under the conditions of 100 DEG C, obtain porous silicon and graphite
The compositionss of alkene, numbering E ".
Embodiment 3 (battery testing)
Using compositionss E4 of embodiment 10 and compositionss E of comparative example 2 " it is assembled into 2032 as negative active core-shell material
Type button lithium ion battery.Electrode material slurry by active material, conductive agent (acetylene black) and binding agent (cmc) in mass ratio
80:10:10 mix.Electrolyte LB303 is LiPF containing 1mol/L6Ethylene carbonate (EC), dimethyl carbonate (DMC),
Diethyl carbonate (DEC) mixed solution, EC:DMC:DEC mass ratio=1:1:1.
The cycle charge discharge electrical property of above-mentioned lithium ion battery is tested using battery test system.Charging and discharging currents are 1C, on
Lower critical voltage is 0.01~1.5V, and circulating cycle number is 1000.Measure battery performance as shown in table 5 below.
Fig. 9 is above-mentioned lithium ion battery specific discharge capacity (Discharge Capacity) and coulombic efficiency (Coulombic
Efficiency) the curve changed with circulating cycle number, the wherein curve E4-a and E4-b respectively lithium-ion electrics containing compositionss E4
The curve that the specific discharge capacity and coulombic efficiency in pond changes with circulating cycle number.Curve E " is E containing compositionss " lithium ion battery
Specific discharge capacity with circulating cycle number curve.As illustrated, the lithium ion battery containing compositionss E4 shows higher electric discharge ratio
Capacity and capability retention.Table 5 illustrate containing active material for the lithium ion battery of E4 specific discharge capacity and cycle efficieny with following
The curve of ring week number change.
Table 5
| Circulating cycle number | 50 | 200 | 400 | 600 | 800 | 1000 |
| Specific discharge capacity mAh/g | 1440 | 1421 | 1362 | 1320 | 1282 | 1250 |
| Capability retention % | 80.4 | 79.4 | 76.1 | 73.7 | 71.6 | 69.8 |
As shown in Fig. 9 and Biao 5, after above-mentioned active material circulates 1000 weeks for the lithium ion battery of E4 under 1C, specific capacity
For 1250mAh/g, more than 99%, capability retention is 69.8% to coulombic efficiency.This explanation compositions E4 is used as lithium ion battery
Negative material, with higher specific capacity and preferable cycle performance.
It is 10 in view of the mass ratio of porous material in compositionss E4 and Graphene:1, i.e. porous material are in compositionss E4
Main component.It can be deduced that the combination of porous material and various conductive materials (such as carbon, conducting polymer) is used as lithium ion
Battery cathode all has higher specific capacity and preferable cycle performance.
There is similar property in view of Si and Ge, it can be deduced that such as the Si elements in above-described embodiment are replaced with into Ge
Element, is obtained in that specific surface area is higher, porous Ge that pore volume is higher, and obtain it is same or like as technique effect.
Finally it should be noted that：Above example is only to illustrate technical scheme rather than a limitation；To the greatest extent
Pipe has been described in detail with reference to preferred embodiment to the present invention, and those of ordinary skill in the art should be understood：Still
The specific embodiment of the present invention can be modified or equivalent is carried out to some technical characteristics；Without deviating from this
The spirit of bright technical scheme, it all should cover in the middle of the technical scheme scope being claimed in the present invention.
Claims (15)
1. a kind of porous material, it contains M simple substance, and M is Si and/or Ge；
The granularity of the porous material is 20~150nm, and porosity is 0.2~0.8, and specific surface area is 15~300m2/g。
2. the porous material of claim 1, it has following one or more feature,
Preferably, the granularity of the porous material be 50~150nm, such as such as 50~130nm, 50~110nm, such as 60~
100nm, then such as 70~90nm；
Preferably, the porosity of the porous material be 0.3~0.8, such as 0.4~0.8, such as 0.5~0.8, such as 0.6~
0.7；
Preferably, the specific surface area of the porous material is 40~300m2/ g, then such as 100~300m2/ g, then such as 150~
300m2/ g, then such as 200~300m2/ g, then such as 230~300m2/ g, then such as 230~270m2/ g, then such as 240~
260m2/g；
Preferably, the apparent density of the porous material is 0.5~2.2g/cm3, such as 0.5~2g/cm3, such as 0.5~1.5g/
cm3, such as 0.6~1.1g/cm3, such as 0.6~0.8g/cm3；
Preferably, the pore size distribution curve of the porous material has characteristic peak in 10~50nm, for example, have characteristic peak in 5~15nm,
For example there is characteristic peak in 15~25nm again, then for example have characteristic peak in 25~35nm；
Preferably, only one of which characteristic peak on the pore size distribution curve of the porous material；
Preferably, in the TEM photos of the 40 of the porous material~500,000 times, loose structure (such as foam-like porous are able to observe that
Structure)；
Preferably, the porous material contains M simple substance more than 50 weight %；
Preferably, the porous material contains M simple substance more than 90 weight %；
Preferably, the porous material contains M simple substance more than 99 weight %；
Preferably, M is Si.
3. a kind of method for preparing porous material, it includes：
I) ball milling raw material M simple substance and the mixture of oxidant, obtain the oxide of M；
M is Si and/or Ge；
Ii) the oxide of heat treatment M；
Iii) the oxide of the M after pickling heat treatment；
Preferably, the porous material is the porous material of claim 1 or 2.
4. method according to claim 3, step i) has following one or more feature：
Preferably, the purity of raw material M simple substance is greater than about 99.5%, preferably greater than 99.9%；
Preferably, raw material M simple substance to be shaped as spherical, near-spherical, bulk, class block, bar-shaped or irregularly shaped；
Preferably, the volume of raw material M simple substance is 1~10mm3, preferably 3~7mm3；
Preferably, raw material M simple substance and the mol ratio of the oxidant are 1:0.8~1.8, such as 1:1.0~1.5, then such as 1:
1.2~1.4.
5. the described method of claim 3, step i) has following one or more feature：
Preferably, the oxidant includes water；
Preferably, ball milling is carried out under vacuum or nonoxidizing atmosphere, and nonoxidizing atmosphere can be inert gas atmosphere, such as argon
Atmosphere；
Preferably, the rotating speed of ball milling is 500~2000r/min, such as 800~1200r/min；
Preferably, the ball radius that ball milling is used are 1~5mm, such as 3~4mm；
Preferably, the material of the abrading-ball that ball milling is used is ZrO2；
Preferably, the pellet mass ratio of ball milling is 1:20；
Preferably, the time of ball milling is 1~5 hour, such as 3~4 hours.
6. method according to claim 3, step i) has following one or more feature：
Preferably, the oxide of the M is MOx, x=0.2~1.8 (such as x=0.5~1.7, such as x=1.0~1.6, then example
Such as x=1.2~1.4)；
Preferably, the oxide of the M is non-crystalline material；
Preferably, the oxide of the M is that granularity is 50~200nm, such as 50~150nm；
Preferably, in the TEM photos of the oxide of the M, without obvious crystal structure；
Preferably, it is have steamed bun peak in the range of 10~40 ° at 2 θ angles in the XRD curves of the oxide of the M；
Preferably, the oxide of the M is with the XRD curves shown in the curve b such as Fig. 2；
Preferably, the oxide of the M is in Raman spectrogram, in 475~500cm of wavelength-1Position have peak.
7. method according to claim 3, step ii) there is following one or more feature：
Preferably, heat treatment is carried out under vacuum or nonoxidizing atmosphere, and nonoxidizing atmosphere is, for example, inert gas atmosphere, e.g.
The gaseous mixture atmosphere of argon and hydrogen, the content of hydrogen is 1~3 volume % in preferred nonoxidizing atmosphere；
Preferably, the temperature of heat treatment is 500~1500 DEG C, e.g. 800~1200 DEG C；
Preferably, the time of heat treatment is 1~5 hour, such as 3~5 hours.
8. the method described in claim 3, step iii) there is following one or more feature：
Preferably, the acid that pickling is used includes Fluohydric acid., and the concentration of Fluohydric acid. is preferably 0.1~1mol/L, further preferably for 0.3~
0.8mol/L；
Preferably, the time of pickling is more than 0.1 hour, preferably 0.3~0.7 hour；
Preferably, the one or multi-step in being filtered, washed and dried also is included after pickling.
9. a kind of compositionss, the porous material containing conductive compositions and claim 1 or 2；
Preferably, the conductive compositions are carbon and/or conducting polymer；
Preferably, the carbon is selected from graphite, hard carbon, soft carbon, white carbon black, activated carbon, C60, Graphene, graphene oxide or nano-sized carbon
One or more in pipe；
Preferably, the compositionss are the porous material of claim 1 or 2 and the product of conductive compositions ball milling mixing.
10. compositionss of claim 9, it has following one or more feature：
Preferably, the compositionss specific surface area is 2~30m2/ g, such as 5~30m2/ g, then such as 10~30m2/ g, then for example
15~30m2/ g, then such as 20~30m2/g；
Preferably, in the compositionss, M element is respectively 1 with the mass ratio of carbon:0.01~10, such as 1:0.1~0.2；
Preferably, electric discharge of the compositionss as lithium ion battery negative material, under 1C electric current densities, after circulating 1000 weeks
Specific capacity is 1000~1500mAh/g, such as 1100~1400mAh/g, then such as 1200~1300mAh/g.
The preparation method of the compositionss of 11. claim 9 or 10, it is comprised the following steps：
Ball milling after the porous material of claim 1 or 2 is mixed with the conductive compositions.
The method of 12. claim 11, it has following one or more feature：
Preferably, ball milling is carried out under vacuum or nonoxidizing atmosphere, and nonoxidizing atmosphere can be inert gas atmosphere, such as argon
Atmosphere；
Preferably, the rotating speed of ball milling is 300~800r/min, such as 500r/min；
Preferably, the time of ball milling is 1~3 hour, such as 2 hours；
Preferably, ball radius are 3~8mm, such as 5mm；
Preferably, the material of abrading-ball is ZrO2；
Preferably, raw material Si or raw material Ge and the mass ratio of abrading-ball are 1:15~25, such as 1:20.
The porous material of 13. claim 1 or 2, or the compositionss of claim 9 or 10 are used as the purposes of electrode material；
Preferably, the electrode material is lithium ion battery negative material.
A kind of 14. electrode materials, it is included described in porous material or claim 9 or 10 described in claim 1 or 2
Compositionss；
Preferably, the electrode material is lithium ion battery negative material.
A kind of 15. batteries, it includes the compositionss of the porous material of claim 1 or 2 or claim 9 or 10；
Preferably, the negative material of the battery includes the porous material of claim 1 or 2 or the combination of claim 9 or 10
Thing；
Preferably, the battery is lithium ion battery.
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