CN107195893A - Boron-doped silicon-based negative electrode material for lithium ion battery - Google Patents
Boron-doped silicon-based negative electrode material for lithium ion battery Download PDFInfo
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- CN107195893A CN107195893A CN201710530314.6A CN201710530314A CN107195893A CN 107195893 A CN107195893 A CN 107195893A CN 201710530314 A CN201710530314 A CN 201710530314A CN 107195893 A CN107195893 A CN 107195893A
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 65
- 239000010703 silicon Substances 0.000 title claims abstract description 64
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 21
- 239000007773 negative electrode material Substances 0.000 title abstract 2
- 239000000463 material Substances 0.000 claims abstract description 79
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 20
- 239000010439 graphite Substances 0.000 claims abstract description 19
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002210 silicon-based material Substances 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 238000013329 compounding Methods 0.000 claims abstract description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 33
- 229910052796 boron Inorganic materials 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000010405 anode material Substances 0.000 claims description 14
- 239000002070 nanowire Substances 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 240000007594 Oryza sativa Species 0.000 claims description 3
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 239000003595 mist Substances 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- 238000000713 high-energy ball milling Methods 0.000 claims description 2
- 239000002071 nanotube Substances 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 10
- 239000003513 alkali Substances 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 238000000498 ball milling Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000010406 cathode material Substances 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000000872 buffer Substances 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229910052573 porcelain Inorganic materials 0.000 description 7
- 238000010792 warming Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 239000002322 conducting polymer Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 244000294611 Punica granatum Species 0.000 description 1
- 235000014360 Punica granatum Nutrition 0.000 description 1
- 239000002194 amorphous carbon material Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Composite Materials (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Silicon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a boron-doped silicon-based negative electrode material for a lithium ion battery, which is prepared by compounding boron-doped nano silicon material and graphite, wherein the mass percent of the boron-doped nano silicon material is 3-100%, and the balance is graphite. According to the invention, boron trioxide gradually diffuses to the silicon cathode material in the high-temperature sintering process to replace partial silicon atoms to form substitutional doping, so that the vacancy carrier concentration in the nano silicon material is improved, the intrinsic electronic conductivity of the silicon material is improved, and the graphite buffers the volume expansion of the silicon material. The method has the advantages of simple preparation process, convenient operation, natural and easily-obtained raw materials, low cost, convenient subsequent treatment mode and easy large-scale production.
Description
Technical field
The present invention relates to technical field of lithium ion, more particularly, to a kind of lithium ion battery boron-doping silicon base negative pole
Material.
Background technology
In recent years, as lithium ion battery should in the powerful device such as electric tool, electronic/mixed electrical automobile, energy-accumulating power station
The continuous expansion used, conventional graphite negative pole (372mAh/g) has been difficult to meet demand of the mankind to high energy density cells,
Therefore heat of the lithium ion battery negative material of future generation of graphite as current lithium ion battery correlative study can be substituted by finding
One of point.The theoretical specific capacity of silicon materials be 4200mAh/g, its aboundresources, and will not with electrolyte occur solvent be embedded in altogether
Phenomenon, while intercalation potential is higher, it is safer.But silicon pole material can undergo up to 300% body in charge and discharge process
Product change, so high volumetric expansion are shunk, and are easily caused electrode material crushing, are disengaged with collector, electrodes conduct network
Etc. defect；Volume Changes can also bring the generation on new surface, it is necessary to form new solid-electrolyte interface (SEI) simultaneously, so that
Cause a large amount of consumption to electrolyte, and then cause being greatly lowered for battery cycle life.On the other hand, the electrical conductivity of silicon,
Lithium ion diffusion velocity is below graphite, and this will limit performance of the silicon under the conditions of high current is high-power.
The means such as academic circles at present is mainly mutually combined by nanosizing, with inertia, pore-creating optimize material structure to be lifted
Its chemical property.Such as houd (Chou S, Wang J, Choucair M, et al.Enhanced reversible
lithium storage in a nanosize silicon/graphene composite[J].Electrochemistry
Communications,2010,12(2):Silicon/graphene composite material 303-306.) is prepared for by simple liquid phase method, it is first
Secondary reversible capacity reaches 2158mAh/g.(Jo Y N, Kim Y, Kim J S, the et al.Si-graphite composites such as Kim
as anode materials for lithium secondary batteries[J].Journal of Power
Sources,2010,195(18):Silicon/graphite/amorphous carbon material, material 6031-6036.) is prepared for the method for mechanical ball mill
Expect good conductivity, coulombic efficiency is up to 86.4% first.(Liu N, Lu Z, Zhao J, the et al.A such as Liu
pomegranate-inspired nanoscale design for large-volume-change lithium battery
anodes[J].Nat Nanotechnol,2014,9(3):A kind of pomegranate 187-192.) is prepared using the method for polymer cracking
The nano silicon-based composite of stone structure.One layer of resin pyrolytic carbon of nano-silicon clustered particles Surface coating.This material is in 1A/g electricity
Reversible specific capacity reaches 2350mAh/g first under current density.But these methods are carried using carbon material or conducting polymer
The electron conduction of high silica-base material, but the intrinsic electronic conductivity of silicon materials is not improved.
The content of the invention
In order to solve the phenomenon that the electronic conductivity of above-mentioned silicon materials in itself is relatively low, the invention provides a kind of lithium-ion electric
Pond boron-doping silicon negative material.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of lithium ion battery boron-doping silicon base negative material, the boron-doping silicon base negative material is received by boron doping
Rice silicon materials are formed with graphite compounding, and wherein the mass percent of boron dopen Nano silicon materials is 3-100%, and graphite is surplus.
Further scheme, the boron dopen Nano silicon materials are ground after silicon is well mixed with diboron trioxide,
It is subsequently placed in the tube furnace for be connected with inert atmosphere and is sintered；Finally it is placed in aqueous slkali and soaks after 10min-60min, washes
Wash, filter and dry gained.
Further scheme, the silicon is one kind in nano silicon particles, nano-tube, silicon nanowires, silicon nano thin-film
Or it is several.
Further scheme, the silicon is mixed with the hybrid mode of diboron trioxide for liquid phase, mechanical lapping, planetary ball
One or more in mill, high-energy ball milling.
Further scheme, the quality of the diboron trioxide accounts for the 1%-10% of siliceous amount.
Further scheme, the sintering temperature is 800 DEG C -1200 DEG C, and programming rate is 5 DEG C/min-20 DEG C/min, sintering
Time is 1-12h.
Further scheme, the aqueous slkali is NaOH solution, KOH solution, Ba (OH)2Solution, Ca (OH)2One in solution
Plant or several.
Further scheme, the graphite is native graphite, Delanium or carbonaceous mesophase spherules.
Further scheme, the boron-doping silicon base negative material be by after boron dopen Nano silicon materials spray drying granulation with
Graphite is mixed, or mist projection granulating is formed again after boron dopen Nano silicon materials are mixed with graphite.
The boron-doping silicon base negative material of the present invention is with needing offer one according to capacity by boron doped nano silicon material
Certainty ratio and play buffering expansion graphite material compounding form.
Compared with prior art, the present invention has advantages below：
Prior art is mainly to be led by improving the electronics of silica-base material with conductive charcoal, conducting polymer or metal composite
Electrically；And the present invention is the electronic conductivity from silicon materials in itself, by boron atom under the high temperature conditions to silicium cathode material
Material gradually spreads, and substitutes part silicon atom, forms instead type doping, so that nano silicon material Vacancy carrier concentration is improved,
And then improve the native electronic conductance of silicon materials.It can also compound certain graphite according to capacity needs and carry out padded coaming simultaneously
Volumetric expansion.
The present invention prepares boron-doping silicon negative material by the way of high temperature sintering, and its preparation technology is simple, easy to operate,
Raw material is naturally easy to get, and cost is low, and subsequent treatment mode is convenient.
Boron-doping silicon material prepared by the present invention can be applied not only to negative electrode of lithium ion battery field, can also be applied to
The fields such as fieldtron, solar device, luminescent device and sensor component.
Brief description of the drawings
Fig. 1 is the electronic conductivity comparison diagram of boron-doping silicon nano wire prepared by embodiment 1-2 and comparative example silicon nanowires.
Fig. 2 is the EDS figures of boron dopen Nano silicon grain prepared by embodiment 3.
Fig. 3 is the charging and discharging curve figure of nano-silicon and boron dopen Nano silicon grain in embodiment 3.
Fig. 4 is the SEM figures of silicon based anode material prepared by embodiment 4
Fig. 5 is the first charge-discharge curve of silicon based anode material prepared by embodiment 4
Embodiment
For the ease of understanding the present invention, present invention work more comprehensively, is meticulously described below in conjunction with embodiment, but this hair
Bright protection domain is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art
It is identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention
Protection domain.
Except there is a special instruction, the various reagents used in the present invention, raw material be can be commercially commodity or
Person can pass through product made from known method.
Embodiment 1：
1g diboron trioxides and 10g silicon nanowires are added in mortar, grinding makes material be uniformly dispersed, and material is put into porcelain
In boat, it is put into the tube furnace for being connected with nitrogen, 900 DEG C of sintering 1h is raised to by 5 DEG C/min of programming rate.Room temperature is cooled to, will
0.5h is soaked in material immersion sodium hydroxide solution, is washed with deionized and dries, obtaining silicon based anode material, (boron-doping silicon is received
Rice noodles).
The electrochemical property test of silicon based anode material, its conductance are carried out using two probes with characteristic of semiconductor analysis system
Rate is as shown in table 1 and Fig. 1.The electronic conductivity that the boron-doping silicon nano-material after 1h is sintered at 900 DEG C is 5.2 × 10-4S/
Cm, so silicon based anode material prepared by the present invention improves electronic conductivity after being adulterated through boron.
Comparative example 1：
With silicon nanowire material as a comparison, the same chemical property that material is carried out using characteristic of semiconductor analysis system
Test, it can be found that undoped with silicon nanowire material electronic conductivity be 1.1 × 10-7S/cm。
Embodiment 2：
1g diboron trioxides and 10g silicon nanowires are added in mortar, grinding makes material be uniformly dispersed, and material is put into porcelain
In boat, in the tube furnace for being put into same nitrogen, it is warming up to by 5 DEG C/min of programming rate at 1000 DEG C and sinters 1h.It is cooled to room temperature,
Immerse the material into and 0.5h is soaked in sodium hydroxide solution, be washed with deionized and dry, obtain silicon based anode material (boron-doping silicon
Nano wire).
The electrochemical property test of material, its electrical conductivity such as table 1 are carried out using two probes with characteristic of semiconductor analysis system
With shown in Fig. 1.The electronic conductivity that the boron-doping silicon nano-material after 1h is sintered at 1000 DEG C is 0.21S/cm.Pass through contrast
It can be found that the electronic conductivity of material gets a promotion after boron doping, and increase to a certain extent with the rise of temperature
Greatly.
The electronic conductivity that table 1 adulterates with undoped silicon nano wire
| Material | Electrical conductivity |
| Comparative example 1 | 1.1×10-7S/cm |
| Embodiment 1 | 5.2×10-4S/cm |
| Embodiment 2 | 0.21S/cm |
Embodiment 3：
1g diboron trioxides are added in mortar with 10g silicon nanoparticles, and grinding makes material be uniformly dispersed, and material is put into porcelain
In boat, in the tube furnace for being put into same nitrogen, it is warming up to by 20 DEG C/min of programming rate at 1000 DEG C and sinters 1h.It is cooled to room
Temperature, immerses the material into and 0.5h is soaked in sodium hydroxide solution, is washed with deionized and dries, obtaining silicon based anode material, (boron is mixed
Miscellaneous nano-silicon).
The EDS power spectrums that Fig. 2 is, it is found that with the presence of obvious boron element in material.
By nano-silicon：SP：LA133=8:1:1 ratio carries out conjunction slurry, coating, assembles CR2016 button cells, and electrolyte makes
With 1mol/L LiPF6 EC+DMC solution, and carry out electrochemical property test.
The charging and discharging curve figure of nano-silicon and boron dopen Nano silicon is illustrated in figure 3, from figure 3, it can be seen that the head of nano-silicon
Secondary charge specific capacity is 1650mAh/g, head effects only 45.8%；The initial charge specific capacity of boron dopen Nano silicon is 2244mAh/
G, head effect be 62.3% because in charge and discharge process the volumetric expansion and contraction of nano-silicon cause material and around SP
Lose electrical contact, but the electronic conductivity of boron dopen Nano silicon is of a relatively high, thus pole piece internal resistance is smaller, chemical property compared with
It is good.
Embodiment 4：
0.1g diboron trioxides are added in mortar with 10g silicon nanoparticles, and grinding makes material be uniformly dispersed, and material is put into
In porcelain boat, in the tube furnace for being put into same nitrogen, it is warming up to by 10 DEG C/min of programming rate at 800 DEG C and sinters 12h.It is cooled to room
Temperature, immerses the material into and 0.5h is soaked in sodium hydroxide solution, is washed with deionized and dry boron dopen Nano silicon materials.
Take 3g boron dopen Nano silicon materials to be dissolved in absolute ethyl alcohol, carry out spray drying granulation after, then with 97g Delaniums
Mixed, obtain silicon based anode material.
Fig. 4 schemes for the SEM of silicon based anode material manufactured in the present embodiment, and wherein spheric granules is that boron dopen Nano silicon is laggard
Row mist projection granulating is formed.
By above-mentioned material：SP：LA133=8:1:1 ratio carries out conjunction slurry, coating, assembles CR2016 button cells, electrolyte
Using 1mol/L LiPF6 EC+DMC solution, and carry out electrochemical property test.It is illustrated in figure 5 silicon manufactured in the present embodiment
The charging and discharging curve figure of base negative material, its initial charge specific capacity is 421.8mAh/g, and first discharge specific capacity is
460.1mAh/g, head effect reach 91.7%.Because the electronic conductivity of boron dopen Nano silicon is of a relatively high, thus in pole piece
Resistance is smaller, while the volume exapnsion of graphite padded coaming, therefore chemical property is preferable.
Embodiment 5：
0.5g diboron trioxides are added in mortar with 10g silicon nanoparticles, and grinding makes material be uniformly dispersed, and material is put into
In porcelain boat, in the tube furnace for being put into same nitrogen, it is warming up to by 15 DEG C/min of programming rate at 1200 DEG C and sinters 10h.It is cooled to
Room temperature, immerses the material into and 0.8h is soaked in potassium hydroxide solution, is washed with deionized and dry boron dopen Nano silicon materials.
Take 5g to obtain boron dopen Nano silicon materials to be dissolved in absolute ethyl alcohol, carry out spray drying granulation, and with 95g Delaniums
Mixed, obtain silicon based anode material.
Embodiment 6：
0.5g diboron trioxides are added in mortar with 10g silicon nanowires, and grinding makes material be uniformly dispersed, and material is put into porcelain
In boat, in the tube furnace for being put into same nitrogen, it is warming up to by 5 DEG C/min-20 DEG C/min of programming rate at 1000 DEG C and sinters 1h.It is cold
But to room temperature, immerse the material into and 1h is soaked in aqua calcis, be washed with deionized and dry boron dopen Nano silicon material
Material.Take 10g to obtain boron dopen Nano silicon materials to be dissolved in absolute ethyl alcohol, and add 90g native graphites and mixed, spray drying is made
Grain, obtains silicon based anode material.
Embodiment 7：
1g diboron trioxides are added in mortar with 10g silicon nano thin-film, and grinding makes material be uniformly dispersed, and material is put into porcelain
In boat, in the tube furnace for being put into same nitrogen, it is warming up to by 5 DEG C/min-20 DEG C/min of programming rate at 1000 DEG C and sinters 1h.It is cold
But to room temperature, immerse the material into and 0.5h is soaked in barium hydroxide solution, be washed with deionized and dry boron dopen Nano silicon
Material.Take 60g to obtain boron dopen Nano silicon materials to be dissolved in absolute ethyl alcohol, and add 40g carbonaceous mesophase spherules and mixed, sprayed
Drying-granulating, obtains silicon based anode material.
Moreover, it will be appreciated that although the present specification is described in terms of embodiments, not each embodiment is only wrapped
Containing an independent technical scheme, this narrating mode of specification is only that for clarity, those skilled in the art should
Using specification as an entirety, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
It may be appreciated other implementations.
Claims (9)
1. a kind of lithium ion battery boron-doping silicon base negative material, it is characterised in that：The boron-doping silicon base negative material is
Formed by boron dopen Nano silicon materials with graphite compounding, wherein the mass percent of boron dopen Nano silicon materials is 3-100%, stone
Ink is surplus.
2. a kind of lithium ion battery boron-doping silicon base negative material according to claims 1, it is characterised in that：It is described
Boron dopen Nano silicon materials are ground after silicon is well mixed with diboron trioxide, are subsequently placed in the pipe for being connected with inert atmosphere
It is sintered in formula stove；Finally it is placed in aqueous slkali and soaks after 10min-60min, washing, filtering simultaneously dries gained.
3. the lithium ion battery boron-doping silicon base negative material according to claims 2, it is characterised in that：The silicon is
One or more in nano silicon particles, nano-tube, silicon nanowires, silicon nano thin-film.
4. the lithium ion battery boron-doping silicon base negative material according to claims 2, it is characterised in that：The silicon with
The hybrid mode of diboron trioxide is the one or more in liquid phase mixing, mechanical lapping, planetary type ball-milling, high-energy ball milling.
5. the lithium ion battery boron-doping silicon base negative material according to claims 2, it is characterised in that：Three oxygen
The quality for changing two boron accounts for the 1%-10% of siliceous amount.
6. the lithium ion battery boron-doping silicon base negative material according to claims 2, it is characterised in that：The sintering
Temperature is 800 DEG C -1200 DEG C, and programming rate is 5 DEG C/min-20 DEG C/min, and sintering time is 1-12h.
7. the lithium ion battery boron-doping silicon base negative material according to claims 2, it is characterised in that：The alkali soluble
Liquid is NaOH solution, KOH solution, Ba (OH)2Solution, Ca (OH)2One or more in solution.
8. the lithium ion battery boron-doping silicon base negative material according to claims 1, it is characterised in that：The graphite
For native graphite, Delanium or carbonaceous mesophase spherules.
9. the lithium ion battery boron-doping silicon base negative material according to claims 1, it is characterised in that：The boron is mixed
Miscellaneous silicon based anode material is will to be mixed after boron dopen Nano silicon materials spray drying granulation with graphite, or boron doping is received
Rice silicon materials mixed with graphite after again mist projection granulating form.
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