CN109461921A - A kind of preparation method based on modified lithium ion battery silicon-base alloy composite negative pole material - Google Patents
A kind of preparation method based on modified lithium ion battery silicon-base alloy composite negative pole material Download PDFInfo
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- CN109461921A CN109461921A CN201811332111.7A CN201811332111A CN109461921A CN 109461921 A CN109461921 A CN 109461921A CN 201811332111 A CN201811332111 A CN 201811332111A CN 109461921 A CN109461921 A CN 109461921A
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 112
- 239000000956 alloy Substances 0.000 title claims abstract description 112
- 239000000463 material Substances 0.000 title claims abstract description 105
- 239000002131 composite material Substances 0.000 title claims abstract description 104
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical class [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 229910018619 Si-Fe Inorganic materials 0.000 claims abstract description 156
- 229910008289 Si—Fe Inorganic materials 0.000 claims abstract description 156
- 238000000498 ball milling Methods 0.000 claims abstract description 102
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 70
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- 229910021389 graphene Inorganic materials 0.000 claims abstract description 50
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 50
- 239000007789 gas Substances 0.000 claims abstract description 32
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- 239000011261 inert gas Substances 0.000 claims abstract description 28
- 238000012216 screening Methods 0.000 claims abstract description 28
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- 239000000843 powder Substances 0.000 claims description 36
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- 238000001816 cooling Methods 0.000 claims description 23
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
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- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 17
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 10
- 239000007773 negative electrode material Substances 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
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- 239000012895 dilution Substances 0.000 claims description 6
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- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
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- 238000000034 method Methods 0.000 abstract description 30
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- 230000007547 defect Effects 0.000 abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 22
- 229910052710 silicon Inorganic materials 0.000 description 19
- 239000010703 silicon Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
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- 239000011149 active material Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
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- 238000005275 alloying Methods 0.000 description 2
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- 239000010406 cathode material Substances 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910005347 FeSi Inorganic materials 0.000 description 1
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- 229910008318 Si—M Inorganic materials 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
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- 229910052787 antimony Inorganic materials 0.000 description 1
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
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- 238000007670 refining Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 238000013517 stratification Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 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
- 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
-
- 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
-
- 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
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of lithium ion battery silicon-base alloy composite negative pole materials and preparation method thereof, are related to technical field of lithium ion.This method comprises: being modified to obtain Si-Fe/ pitch predecessor, Si-Fe/SBR predecessor, Si-Fe/ pitch/CNTs predecessor, any modified product in Si-Fe/ pitch/graphene predecessor to Si-Fe alloy using ball milling, carbon coating, doping one of conductive agent or various ways；This kind of modified product is put in tube furnace, after being warming up to preset temperature under inert gas argon gas shielded with scheduled rate, heat preservation preset time is pyrolyzed, and is cooled to screening after room temperature with the furnace and obtained lithium ion battery silicon-base alloy composite negative pole material.The composite negative pole material that this method is prepared can solve existing Si-Fe alloy and have the defects that intrinsic, can effectively improve its chemical property.
Description
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of based on modified lithium ion battery silicon substrate conjunction
The preparation method of golden composite negative pole material.
Background technique
Lithium ion battery technology is the key that develop new-energy automobile industry.With large-scale commercial new-energy automobile
Development, to the energy density of lithium-ion-power cell, rapid charging performance, security performance and cost etc., more stringent requirements are proposed.?
In terms of the energy density of battery, the year two thousand twenty is arrived, strives that Novel lithium ion power battery monomer specific energy will be more than 300 watt-hours/public affairs
Jin.And existing it is difficult have biggish breakthrough in energy density using graphite as the lithium-ion-power cell of cathode at present, it is difficult to full
The requirement of foot generation high-energy-density lithium-ion-power cell.Therefore, the silica-base material with high theoretical capacity is sent out as emphasis
The negative electrode material of exhibition.
But there are serious volume expansion (~300%), huge volume effects in charge and discharge process for silicium cathode material
It answers and lower conductivity limits its commercial applications, be mainly shown as that the volume expansion generated after the embedding lithium of silicon easily causes in electrode
The dusting and rupture of active particle, so that being lost between active material particle and particle and between active material and collector
Electrical contact, capacitance loss are greatly lowered.Meanwhile electrode surface can not form stable solid electrolyte interface film (SEI) and
Cause biggish irreversible capacity.For these problems, domestic and foreign scholars are by obtaining fine uniform for silicon particle nanosizing
Primary particle solves the stress and pulverizing problem of silicon particle using the synergistic effect of charge and discharge lattice variations.And to silicon particle
Surface is modified, and using the network structure and stratification pore structure of carbon material, provides electronics conduction path and ion transmission is logical
The volume expansion of silicon can also be accommodated while road, core-shell structure constructed by silicon and carbon material can guarantee that the structure of material is steady
Qualitative and electrode integrality.In addition, the compound Si-M system for preparing silicon is also modified one of the effective measures of silica-base material,
Active material silicon is dispersed in lithium inert metal M matrix, and M matrix can inhibit volume change of the silicon in charge and discharge and mention
The conductivity of high silicon.Such as the FeSi in Si-Fe system2It can be used as buffer layer and conductive materials mutually to improve the conduction of material
Property and maintain structure stability.Silicon and the silicon intermetallic compound of metal composite can be such that the cycle performance of silica-base material obtains
A degree of improvement, but the biggish capacity attenuation of the composite material is still a main problem urgently to be resolved.
CN103280555A discloses a kind of lithium ion battery silicon-base alloy negative electrode material and preparation method thereof and lithium-ion electric
High-purity silicon powder and metal antimony powder are uniformly mixed by certain mol proportion and are put into vacuum ball grinder, while ball milling controlling agent is added by pond,
It is filled with inert protective gas, 10~15h of high-energy ball milling, heating in vacuum removes ball milling controlling agent, obtains the conjunction of lithium ion battery silicon substrate
Golden negative electrode material.Wherein, Si0.8Sb alloy anode is with current density 0.05mA/cm2, 0~2.0V of voltage range progress charge and discharge,
First discharge specific capacity reaches 1288.4mAh/g, and after 50 weeks circulations, specific discharge capacity maintains 596.4mAh/g, reversible appearance
Measuring conservation rate is 59.5%.
CN101510601B discloses a kind of preparation method of silicon stannum alloy cathode material in lithium ion battery, and this method is with silicon
Oxide ball be template, be first prepared the silicide intermediate for being coated with tin-oxide, reduction obtains nanometer after carbon coating
The negative electrode material of silicon stannum alloy, initial discharge capacity can reach 750mAh/g, and the capacity after 100 weeks circulations is 600mAh/g.
CN108346788A discloses a kind of preparation method of carbon coating Antaciron composite negative pole material.By to Si-
Fe alloy carries out carbon coating, or a certain amount of conductive agent of addition is modified, and compound by the obtained Si-Fe/C of mechanical ball mill pyrolysismethod
Negative electrode material.Play the role of enhancing electron conduction based on organic carbon source pyrolytic carbon, conductive agent and buffer silicon bulk effect, reaches
The purpose of the first charge-discharge efficiency and cyclical stability that improve composite material is arrived.But for meet high-energy density lithium from
The requirement of sub- power battery, there is still a need for further promoted for the chemical property of Si-Fe/C composite negative pole material.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of lithium ion battery silicon base alloy composite materials, this preparation sides
Method for Si-Fe alloy have the defects that it is intrinsic, using ball milling, carbon coating, adulterate conductive agent means to Si-Fe alloy carry out
It is modified, to effectively improve its chemical property.
Another object of the present invention is to provide a kind of lithium ion battery silicon base alloy composite materials, pass through above system
Preparation Method is prepared.Therefore, the electrochemical performance of the lithium ion battery silicon base alloy composite materials.
The present invention solves its technical problem and adopts the following technical solutions to realize.
The present invention proposes a kind of preparation method based on modified lithium ion battery silicon-base alloy composite negative pole material, packet
It includes and Si-Fe alloy is modified to obtain Si-Fe/ drip using one of ball milling, carbon coating, doping conductive agent or various ways
Green predecessor, Si-Fe/SBR predecessor, Si-Fe/ pitch/CNTs predecessor, appointing in Si-Fe/ pitch/graphene predecessor
A kind of modified product；Modified product is put in tube furnace, is warming up under inert gas argon gas shielded with scheduled rate default
After temperature, heat preservation preset time is pyrolyzed, and cools to room temperature with the furnace, lithium ion battery silicon-base alloy Compound Negative is obtained after screening
Pole material.
The present invention proposes a kind of preparation method based on modified lithium ion battery silicon-base alloy composite negative pole material, leads to
Above preparation method is crossed to be prepared.
A kind of beneficial effect of lithium ion battery silicon-base alloy composite negative pole material of the embodiment of the present invention and preparation method thereof
Fruit is:
The lithium ion battery silicon-base alloy composite negative pole material being prepared by this method exists solid for Si-Fe alloy
Some defects are modified Si-Fe alloy using the means of ball milling, carbon coating, doping conductive agent, can effectively improve its electricity
Chemical property.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Below to a kind of lithium ion battery silicon-base alloy composite negative pole material of the embodiment of the present invention and preparation method thereof into
Row illustrates.
The embodiment provides a kind of systems based on modified lithium ion battery silicon-base alloy composite negative pole material
Preparation Method comprising:
Si-Fe alloy is modified to obtain using one of ball milling, carbon coating, doping conductive agent or various ways
Si-Fe/ pitch predecessor, Si-Fe/SBR predecessor, Si-Fe/ pitch/CNTs predecessor, Si-Fe/ pitch/graphene forerunner
Any modified product in object；
Modified product is put in tube furnace, preset temperature is warming up to scheduled rate under inert gas argon gas shielded
Afterwards, heat preservation preset time is pyrolyzed, and cools to room temperature with the furnace, lithium ion battery silicon-base alloy composite negative pole material is obtained after screening
Material.
In detail, in an embodiment of the present invention, this method for Si-Fe alloy have the defects that it is intrinsic, using ball milling,
Carbon coating, the means for adulterating conductive agent are modified Si-Fe alloy and can effectively improve its chemical property.
Further, in the preferred embodiment, the preparation of Si-Fe/ pitch predecessor specifically includes:
The ferro-silicon alloy powder that 14~50g average grain diameter is 56 μm is weighed, 150mL deionized water is added and is placed in ball mill
Ball milling is carried out, the Antaciron slurry that mean particle size is 0.58~7.7 μm is obtained；Wherein, ball milling is placed in stirring-type ball milling
It is carried out in machine, and is the zirconium ball for using diameter as 0.3~1.2mm of φ, ratio of grinding media to material 20:1, the ball milling 1h at 2500rpm；By ball
Antaciron slurry after mill is put into vacuum oven and in 120 DEG C of at a temperature of dry 12h；By the Antaciron after drying
The pitch of addition 30% obtains Si-Fe/ pitch predecessor with 100rpm mixing 12h on batch mixer after powder is ground up, sieved.
Preferably, after the citric acid of 5g can also being added in the ferro-silicon alloy powder that 14~50g average grain diameter is 56 μm, then
Addition 150mL deionized water, which is placed in ball mill, carries out ball milling, obtains the ferrosilicon that mean particle size is 0.23~1.0 μm and closes
Gold conductor.Citric acid is used as dispersing agent, and the addition of dispersing agent can solve the agglomeration traits of powder granule, composite material
Discharge capacity is promoted.When pitch and Si-Fe alloy ball milling simultaneously, come into full contact with covering with particle is wrapped by, favorably
In the performance of composite material capacity.But the material after agitated formula ball mill ball milling is since Si phase is reduced, FeSi2Mutually increase, and
Si is converted into amorphous reason from crystalline state, and the discharge capacity of composite material is lower.
Further, in the preferred embodiment, the preparation of Si-Fe/ pitch predecessor also specifically includes:
After weighing ferro-silicon alloy powder, the citric acid of 5g and the pitch of 15g that 14~50g average grain diameter is 56 μm, it is added
150mL deionized water, which is placed in ball mill, carries out ball milling, obtains Si-Fe/ pitch predecessor slurry；Wherein, ball milling, which is placed in, stirs
It mixes and is carried out in formula ball mill, and be the zirconium ball for using diameter as 0.3~1.2mm of φ, ratio of grinding media to material 20:1, the ball at 2500rpm
Grind 1h；Si-Fe/ pitch predecessor slurry is put into vacuum oven at 120 DEG C, dry 12h after being ground up, sieved, obtains Si-
Fe/ pitch predecessor.
Further, in the preferred embodiment, the preparation of Si-Fe/ pitch predecessor specifically includes: weighing 14
The Antaciron that~50g average grain diameter is 56 μm, the alcohol that 60mL is added, which is placed in ball mill, carries out ball milling, obtains Si-Fe
Slurry；Wherein, ball milling is placed in carries out in planetary ball mill, and is each 50% carbon for using diameter as φ 5mm and φ 3mm
Change tungsten ball, ratio of grinding media to material 20:1, the ball milling 5h at 400rpm；Add again after Si-Fe slurry to be added to the deionized water dilution of 1000mL
Enter the pitch of 12g, and be dried in spraying machine, and 300 DEG C of inlet temperature, 100 DEG C of outlet temperature, obtains Si-Fe/ pitch
Predecessor.
Further, in the preferred embodiment, the preparation of Si-Fe/SBR predecessor specifically includes: weighing 14
The ferro-silicon alloy powder that~50g average grain diameter is 56 μm, the alcohol that 60mL is added, which is placed in ball mill, carries out ball milling, obtains Si-
Fe slurry；Wherein, ball milling is placed in carries out in planetary ball mill, and is use diameter for each the 50% of φ 5mm and φ 3mm
Tungsten-carbide ball, ratio of grinding media to material 20:1, the ball milling 5h at 400rpm；Si-Fe slurry is added after the deionized water dilution of 1000mL again
The butadiene-styrene rubber of 12g is added, and is dried in spraying machine, and 300 DEG C of inlet temperature, 100 DEG C of outlet temperature, obtains Si-
Fe/SBR predecessor.
In detail, in an embodiment of the present invention, butadiene-styrene rubber and pitch are used as covering, using planetary type ball-milling
Machine ball milling material changes covering type, prepares composite material using mechanical ball mill-spray drying pyrolysismethod, can be effectively
The discharge capacity and first charge-discharge efficiency of composite material are improved, while cyclical stability is also further promoted.When
So, in other embodiments of the invention, the type of covering can also be selected further according to demand, of the invention
Embodiment is without limitation.
Further, in the preferred embodiment, Si-Fe/ pitch/CNTs predecessor preparation specifically includes:
The ferro-silicon alloy powder that 14~50g average grain diameter is 56 μm is weighed, the alcohol that 60mL is added, which is placed in ball mill, carries out ball milling, obtains
To Si-Fe slurry；Wherein, ball milling is placed in carries out in planetary ball mill, and is use diameter for each of φ 5mm and φ 3mm
50% tungsten-carbide ball, ratio of grinding media to material 20:1, the ball milling 5h at 400rpm；The deionized water that 1000mL is added in Si-Fe slurry is dilute
The pitch of 12g and 4% carbon nanotube are added after releasing, and after being stirred under vacuum 1h, are dried in spraying machine, and inlet temperature
300 DEG C, 100 DEG C of outlet temperature, obtain Si-Fe/ pitch/CNTs predecessor.
Further, in the preferred embodiment,
The preparation of Si-Fe/ pitch/graphene predecessor specifically includes: weighing the ferrosilicon that 14~50g average grain diameter is 56 μm
Alloyed powder, is added 2%~10% graphene and the alcohol of 30mL is placed in ball mill and carries out ball milling, obtains Si-Fe/ drip
Blueness/graphene slurry；Wherein, ball milling is placed in carries out in planetary ball mill, and is use diameter for φ 5mm and φ 3mm
Each 50% tungsten-carbide ball, ratio of grinding media to material 20:1, the ball milling 5h at 400rpm；Si-Fe/ pitch/graphene slurry is put into vacuum
In drying box, and 80 DEG C at a temperature of dry 12h after obtain Si-Fe/ pitch/graphene predecessor.
In detail, using pitch as covering, graphene conductive material is introduced, composite wood is prepared using mechanical ball mill pyrolysismethod
Material, can also effectively improve the comprehensive electrochemical of composite material.
Further, in the preferred embodiment, lithium ion battery silicon is prepared using Si-Fe/ pitch predecessor
Based alloy composite negative pole material specifically includes: Si-Fe/ pitch predecessor being put in tube furnace, in inert gas argon gas shielded
Under with 5 DEG C/min rate be warming up to 850 DEG C, heat preservation 3h is pyrolyzed, and cooling to screening after room temperature with the furnace, to obtain Si-Fe/C compound
Material；
It prepares lithium ion battery silicon-base alloy composite negative pole material using Si-Fe/SBR predecessor to specifically include: by Si-
Fe/SBR predecessor is put in tube furnace, is warming up to 850 DEG C under inert gas argon gas shielded with 5 DEG C/min rate, keeps the temperature 3h
It is pyrolyzed, screening obtains Si-Fe/C composite material after cooling to room temperature with the furnace；
Lithium ion battery silicon-base alloy composite negative pole material is prepared using Si-Fe/ pitch/CNTs predecessor to specifically include:
Si-Fe/ pitch/CNTs predecessor is put in tube furnace, is warming up under inert gas argon gas shielded with 5 DEG C/min rate
850 DEG C~1050 DEG C, heat preservation 3h is pyrolyzed, and screening obtains Si-Fe/C/CNTs composite material after cooling to room temperature with the furnace；
Lithium ion battery silicon-base alloy composite negative pole material is prepared using Si-Fe/ pitch/graphene predecessor specifically to wrap
It includes: Si-Fe/ pitch/graphene predecessor is put in tube furnace, with 5 DEG C/min rate liter under inert gas argon gas shielded
To 850 DEG C~1050 DEG C, heat preservation 3h is pyrolyzed temperature, and screening obtains Si-Fe/C/ graphene composite wood after cooling to room temperature with the furnace
Material.
It is also desirable to which explanation by refining Si-Fe alloying pellet, can achieve in an embodiment of the present invention
Alleviate the absolute volume degrees of expansion of material；Using organic carbon source covering can make amorphous carbon layer be coated on Si-Fe alloy,
On the one hand Si-Fe alloy and conductive agent surface keep composite material by the mechanical strength of enhancing composite material as binder
Structural stability during removal lithium embedded, on the other hand by further absorbing Si-Fe alloy in electrochemical reaction process
Stress, maintain the stability of electrode structure；It introduces graphene and carbon nanotube can use its high conductivity, Yi Jisuo
The conductive network and amorphous carbon of composition, which are formed, to act synergistically, the common electric conductivity for improving Si-Fe alloy, and extends composite material
Cycle life；Using mechanical ball mill-spray drying process, come into full contact with covering and Si-Fe alloy in slurry, through quick
It is dried to obtain the preferable powder of pattern, is evenly coated at Si-Fe alloying pellet table conducive to the pyrolytic carbon layer of Post isothermal treatment process
Face, to be conducive to improve the cycle performance of material.
The embodiments of the present invention also provide a kind of lithium ion battery silicon-base alloy composite negative pole material, lithium ion battery silicons
Based alloy composite negative pole material passes through the above-mentioned preparation side based on modified lithium ion battery silicon-base alloy composite negative pole material
Method is prepared.Therefore, the electrochemical performance of the lithium ion battery silicon-base alloy composite negative pole material.
Detailed description of the invention
Fig. 1 is the XRD diagram of 10 Antaciron composite material of the embodiment of the present invention.
Fig. 2 is that the SEM of 10 Antaciron composite material of the embodiment of the present invention schemes.
Fig. 3 is the cycle performance and high rate performance curve of 10 Antaciron composite material of the embodiment of the present invention.
With reference to the accompanying drawing, table 1, embodiment and comparative example further retouch feature of the invention and performance work in detail
It states.
Embodiment 1
A kind of lithium ion battery silicon-base alloy composite negative pole material is present embodiments provided, is prepared by the following method
It arrives:
(1) weighing 50g average grain diameter is 56 μm of ferro-silicon alloy powders, and 150mL deionized water is added, is placed in stirring ball mill
It carries out ball milling and obtains the Antaciron slurry that mean particle size is 0.58 μm；Wherein, ball milling uses diameter for the zirconium of φ 1.2mm
Ball, ratio of grinding media to material 20:1, the ball milling 1h at 2500rpm；
(2) slurry is put into vacuum oven at 120 DEG C, dries 12h；
(3) after being ground up, sieved, 30% pitch is added on batch mixer with 100rpm mixing 12h, obtains Si-Fe/ pitch
Predecessor；
(4) predecessor is put in tube furnace, is warming up to 850 DEG C under inert gas argon gas shielded with 5 DEG C/min rate,
Heat preservation 3h is pyrolyzed, and screening obtains Si-Fe/C composite material after cooling to room temperature with the furnace.
Embodiment 2
A kind of lithium ion battery silicon-base alloy composite negative pole material is present embodiments provided, is prepared by the following method
It arrives:
(1) weighing 50g average grain diameter is 56 μm of ferro-silicon alloy powders, and 150mL deionized water is added, is placed in stirring ball mill
It carries out ball milling and obtains the Antaciron slurry that mean particle size is 4.24 μm；Wherein, ball milling uses diameter for φ 0.8mm
Zirconium ball, ratio of grinding media to material 20:1, the ball milling 1h at 2500rpm；
(2) slurry is put into vacuum oven at 120 DEG C, dries 12h；
(3) after being ground up, sieved, 30% pitch is added on batch mixer with 100rpm mixing 12h, obtains Si-Fe/ pitch
Predecessor；
(4) predecessor is put in tube furnace, is warming up to 850 DEG C under inert gas argon gas shielded with 5 DEG C/min rate,
Heat preservation 3h is pyrolyzed, and screening obtains Si-Fe/C composite material after cooling to room temperature with the furnace.
Embodiment 3
A kind of lithium ion battery silicon-base alloy composite negative pole material is present embodiments provided, is prepared by the following method
It arrives:
(1) weighing 50g average grain diameter is 56 μm of ferro-silicon alloy powders, and 150mL deionized water is added, is placed in stirring ball mill
It carries out ball milling and obtains the Antaciron slurry that mean particle size is 4.28 μm；Wherein ball milling uses diameter for φ 0.6mm
Zirconium ball, ratio of grinding media to material 20:1, the ball milling 1h at 2500rpm.
(2) slurry is put into vacuum oven at 120 DEG C, dries 12h；
(3) after being ground up, sieved, 30% pitch is added on batch mixer with 100rpm mixing 12h, obtains Si-Fe/ pitch
Predecessor；
(4) predecessor is put in tube furnace, is warming up to 850 DEG C under inert gas argon gas shielded with 5 DEG C/min rate,
Heat preservation 3h is pyrolyzed, and screening obtains Si-Fe/C composite material after cooling to room temperature with the furnace.
Embodiment 4
A kind of lithium ion battery silicon-base alloy composite negative pole material is present embodiments provided, is prepared by the following method
It arrives:
(1) weighing 50g average grain diameter is 56 μm of ferro-silicon alloy powders, and 150mL deionized water is added, is placed in stirring ball mill
It carries out ball milling and obtains the Antaciron slurry that mean particle size is 7.70 μm；Wherein, ball milling uses diameter for φ 0.3mm
Zirconium ball, ratio of grinding media to material 20:1, the ball milling 1h at 2500rpm；
(2) slurry is put into vacuum oven at 120 DEG C, dries 12h；
(3) after being ground up, sieved, 30% pitch is added on batch mixer with 100rpm mixing 12h, obtains Si-Fe/ pitch
Predecessor；
(4) predecessor is put in tube furnace, is warming up to 850 DEG C under inert gas argon gas shielded with 5 DEG C/min rate,
Heat preservation 3h is pyrolyzed, and screening obtains Si-Fe/C composite material after cooling to room temperature with the furnace
Embodiment 5
A kind of lithium ion battery silicon-base alloy composite negative pole material is present embodiments provided, is prepared by the following method
It arrives:
(1) weighing 50g average grain diameter is 56 μm of ferro-silicon alloy powders, 5g citric acid, and 150mL deionized water is added, is placed in and stirs
It mixes formula ball mill progress ball milling and obtains the Antaciron slurry that mean particle size is 0.23 μm；Wherein, ball milling is using diameter
For the zirconium ball of φ 0.8mm, ratio of grinding media to material 20:1, the ball milling 1h at 2500rpm；
(2) slurry is put into vacuum oven at 120 DEG C, dries 12h；
(3) after being ground up, sieved, 30% pitch is added on batch mixer with 100rpm mixing 12h, obtains Si-Fe/ pitch
Predecessor；
(4) predecessor is put in tube furnace, is warming up to 850 DEG C under inert gas argon gas shielded with 5 DEG C/min rate,
Heat preservation 3h is pyrolyzed, and screening obtains Si-Fe/C composite material after cooling to room temperature with the furnace.
Embodiment 6
A kind of lithium ion battery silicon-base alloy composite negative pole material is present embodiments provided, is prepared by the following method
It arrives:
(1) weighing 35g average grain diameter is 56 μm of ferro-silicon alloy powders, 15g pitch, and 150mL deionization is added in 5g citric acid
Water is placed in stirring ball mill progress ball milling and obtains Si-Fe/ pitch predecessor slurry；Wherein, ball milling is to use diameter for φ
The zirconium ball of 0.8mm, ratio of grinding media to material 20:1, the ball milling 1h at 2500rpm；
(2) slurry is put into vacuum oven at 120 DEG C, dries 12h；
(3) after being ground up, sieved, Si-Fe/ pitch predecessor is obtained, predecessor is put in tube furnace, in inert gas argon
850 DEG C are warming up to 5 DEG C/min rate under gas shielded, heat preservation 3h is pyrolyzed, and screening obtains Si- after cooling to room temperature with the furnace
Fe/C composite material.
Embodiment 7
A kind of lithium ion battery silicon-base alloy composite negative pole material is present embodiments provided, is prepared by the following method
It arrives:
(1) weighing 40g average grain diameter is 56 μm of ferro-silicon alloy powders, and 60mL alcohol is added, and is placed in planetary ball mill progress
Ball milling obtains Si-Fe slurry；Wherein, ball milling is to use diameter for the tungsten-carbide ball of φ 5mm and φ 3mm each 50%, ratio of grinding media to material 20:
1, the ball milling 5h at 400rpm；
(2) 12g pitch is added after the dilution of 1000mL deionized water is added, is done in spraying machine after being stirred under vacuum 1h
It is dry, 300 DEG C of inlet temperature, 100 DEG C of outlet temperature, obtain Si-Fe/ pitch predecessor；
(3) predecessor is put into tube furnace, is warming up to 850 DEG C under inert gas argon gas shielded with 5 DEG C/min rate, protected
Warm 3h is pyrolyzed, and screening obtains Si-Fe/C composite material after cooling to room temperature with the furnace.
Embodiment 8
A kind of lithium ion battery silicon-base alloy composite negative pole material is present embodiments provided, is prepared by the following method
It arrives:
(1) weighing 40g average grain diameter is 56 μm of ferro-silicon alloy powders, and 60mL alcohol is added, and is placed in planetary ball mill progress
Ball milling obtains Si-Fe slurry；Wherein, ball milling is to use diameter for the tungsten-carbide ball of φ 5mm and φ 3mm each 50%, ratio of grinding media to material 20:
1, the ball milling 5h at 400rpm；
(2) add 12g butadiene-styrene rubber after the dilution of 1000mL deionized water is added, be stirred under vacuum after 1h in spraying machine into
Row drying, 100 DEG C of outlet temperature, obtains Si-Fe/SBR predecessor by 300 DEG C of inlet temperature；
(3) predecessor is put into tube furnace, is warming up to 850 DEG C under inert gas argon gas shielded with 5 DEG C/min rate, protected
Warm 3h is pyrolyzed, and screening obtains Si-Fe/C composite material after cooling to room temperature with the furnace
Embodiment 9
A kind of lithium ion battery silicon-base alloy composite negative pole material is present embodiments provided, is prepared by the following method
It arrives:
(1) weighing 40g average grain diameter is 56 μm of ferro-silicon alloy powders, and 60mL alcohol is added, and is placed in planetary ball mill progress
Ball milling obtains Si-Fe slurry；Wherein, ball milling is to use diameter for the tungsten-carbide ball of φ 5mm and φ 3mm each 50%, ratio of grinding media to material 20:
1, the ball milling 5h at 400rpm；
(2) it is added after 1000mL deionized water dilutes and adds the carbon nanotube of 12g pitch and 4%, after being stirred under vacuum 1h
It is dried in spraying machine, 300 DEG C of inlet temperature, 100 DEG C of outlet temperature, obtains Si-Fe/ pitch/CNTs predecessor；
(3) predecessor is put into tube furnace, is warming up to 850 DEG C under inert gas argon gas shielded with 5 DEG C/min rate, protected
Warm 3h is pyrolyzed, and screening obtains Si-Fe/C/CNTs composite material after cooling to room temperature with the furnace.
Embodiment 10
A kind of lithium ion battery silicon-base alloy composite negative pole material is present embodiments provided, is prepared by the following method
It arrives:
(1) weighing 14g average grain diameter is 56 μm of ferro-silicon alloy powders, and 4% graphene is added in 6g pitch, then pours into 30mL
Alcohol is placed in planetary ball mill progress ball milling and obtains Si-Fe/ pitch/graphene slurry；Wherein, ball milling be use diameter for
The tungsten-carbide ball of φ 5mm and φ 3mm each 50%, ratio of grinding media to material 20:1, the ball milling 5h at 400rpm；
(2) slurry is put into vacuum oven at 80 DEG C, dries 12h；
(3) after being ground up, sieved, Si-Fe/ pitch/graphene predecessor is obtained.Predecessor is put into tube furnace, in indifferent gas
1050 DEG C are warming up to 5 DEG C/min rate under the protection of body argon gas, and heat preservation 3h is pyrolyzed, and is cooled to the furnace after room temperature to sieve and is obtained
Si-Fe/C/ graphene composite material.
Embodiment 11
A kind of lithium ion battery silicon-base alloy composite negative pole material is present embodiments provided, is prepared by the following method
It arrives:
(1) weighing 14g average grain diameter is 56 μm of ferro-silicon alloy powders, and 4% graphene is added in 6g pitch, then pours into 30mL
Alcohol is placed in planetary ball mill progress ball milling and obtains Si-Fe/ pitch/graphene slurry；Wherein, ball milling be use diameter for
The tungsten-carbide ball of φ 5mm and φ 3mm each 50%, ratio of grinding media to material 20:1, the ball milling 5h at 400rpm；
(2) slurry is put into vacuum oven at 80 DEG C, dries 12h；
(3) after being ground up, sieved, Si-Fe/ pitch/graphene predecessor is obtained；
(4) predecessor is put into tube furnace, is warming up to 900 DEG C under inert gas argon gas shielded with 5 DEG C/min rate, protected
Warm 3h is pyrolyzed, and screening obtains Si-Fe/C/ graphene composite material after cooling to room temperature with the furnace.
Embodiment 12
A kind of lithium ion battery silicon-base alloy composite negative pole material is present embodiments provided, is prepared by the following method
It arrives:
(1) weighing 14g average grain diameter is 56 μm of ferro-silicon alloy powders, and 4% graphene is added in 6g pitch, then pours into 30mL
Alcohol is placed in planetary ball mill progress ball milling and obtains Si-Fe/ pitch/graphene slurry；Wherein, ball milling be use diameter for
The tungsten-carbide ball of φ 5mm and φ 3mm each 50%, ratio of grinding media to material 20:1, the ball milling 5h at 400rpm；
(2) slurry is put into vacuum oven at 80 DEG C, dries 12h；
(3) after being ground up, sieved, Si-Fe/ pitch/graphene predecessor is obtained；
(4) predecessor is put into tube furnace, is warming up to 850 DEG C under inert gas argon gas shielded with 5 DEG C/min rate, protected
Warm 3h is pyrolyzed, and screening obtains Si-Fe/C/ graphene composite material after cooling to room temperature with the furnace.
Embodiment 13
A kind of lithium ion battery silicon-base alloy composite negative pole material is present embodiments provided, is prepared by the following method
It arrives:
(1) weighing 14g average grain diameter is 56 μm of ferro-silicon alloy powders, and 2% graphene is added in 6g pitch, then pours into 30mL
Alcohol is placed in planetary ball mill progress ball milling and obtains Si-Fe/ pitch/graphene slurry；Wherein, ball milling be use diameter for
The tungsten-carbide ball of φ 5mm and φ 3mm each 50%, ratio of grinding media to material 20:1, the ball milling 5h at 400rpm；
(2) slurry is put into vacuum oven at 80 DEG C, dries 12h；
(3) after being ground up, sieved, Si-Fe/ pitch/graphene predecessor is obtained；
(4) predecessor is put into tube furnace, is warming up to 900 DEG C under inert gas argon gas shielded with 5 DEG C/min rate, protected
Warm 3h is pyrolyzed, and screening obtains Si-Fe/C/ graphene composite material after cooling to room temperature with the furnace.
Embodiment 14
A kind of lithium ion battery silicon-base alloy composite negative pole material is present embodiments provided, is prepared by the following method
It arrives:
(1) weighing 14g average grain diameter is 56 μm of ferro-silicon alloy powders, and 6% graphene is added in 6g pitch, then pours into 30mL
Alcohol is placed in planetary ball mill progress ball milling and obtains Si-Fe/ pitch/graphene slurry；Wherein, ball milling uses diameter for φ
The tungsten-carbide ball of 5mm and φ 3mm each 50%, ratio of grinding media to material 20:1, the ball milling 5h at 400rpm；
(2) slurry is put into vacuum oven at 80 DEG C, dries 12h；
(3) after being ground up, sieved, Si-Fe/ pitch/graphene predecessor is obtained；
(4) predecessor is put into tube furnace, is warming up to 900 DEG C under inert gas argon gas shielded with 5 DEG C/min rate, protected
Warm 3h is pyrolyzed, and screening obtains Si-Fe/C/ graphene composite material after cooling to room temperature with the furnace.
Embodiment 15
A kind of lithium ion battery silicon-base alloy composite negative pole material is present embodiments provided, is prepared by the following method
It arrives:
(1) weighing 14g average grain diameter is 56 μm of ferro-silicon alloy powders, and 8% graphene is added in 6g pitch, then pours into 30mL
Alcohol is placed in planetary ball mill progress ball milling and obtains Si-Fe/ pitch/graphene slurry；Wherein, ball milling be use diameter for
The tungsten-carbide ball of φ 5mm and φ 3mm each 50%, ratio of grinding media to material 20:1, the ball milling 5h at 400rpm；
(2) slurry is put into vacuum oven at 80 DEG C, dries 12h；
(3) after being ground up, sieved, Si-Fe/ pitch/graphene predecessor is obtained；
(4) predecessor is put into tube furnace, is warming up to 900 DEG C under inert gas argon gas shielded with 5 DEG C/min rate, protected
Warm 3h is pyrolyzed, and screening obtains Si-Fe/C/ graphene composite material after cooling to room temperature with the furnace
Embodiment 16
A kind of lithium ion battery silicon-base alloy composite negative pole material is present embodiments provided, is prepared by the following method
It arrives:
(1) weighing 14g average grain diameter is 56 μm of ferro-silicon alloy powders, and 10% graphene is added in 6g pitch, then pours into 30mL
Alcohol is placed in planetary ball mill progress ball milling and obtains Si-Fe/ pitch/graphene slurry；Wherein, ball milling be use diameter for
The tungsten-carbide ball of φ 5mm and φ 3mm each 50%, ratio of grinding media to material 20:1, the ball milling 5h at 400rpm；
(2) slurry is put into vacuum oven at 80 DEG C, dries 12h；
(3) after being ground up, sieved, Si-Fe/ pitch/graphene predecessor is obtained；
(4) predecessor is put into tube furnace, is warming up to 900 DEG C under inert gas argon gas shielded with 5 DEG C/min rate, protected
Warm 3h is pyrolyzed, and obtains Si-Fe/C/ graphene composite material after cooling to room temperature screening with the furnace.
Embodiment 17
A kind of lithium ion battery silicon-base alloy composite negative pole material is present embodiments provided, is prepared by the following method
It arrives:
(1) weighing 14g average grain diameter is 56 μm of ferro-silicon alloy powders, and 4% carbon nanotube is added in 6g pitch, then pours into
30mL alcohol is placed in planetary ball mill progress ball milling and obtains Si-Fe/ pitch/CNTs slurry；Wherein, ball milling is using diameter
For the tungsten-carbide ball of φ 5mm and φ 3mm each 50%, ratio of grinding media to material 20:1, the ball milling 5h at 400rpm；
(2) slurry is put into vacuum oven at 80 DEG C, dries 12h；
(3) after being ground up, sieved, Si-Fe/ pitch/CNTs predecessor is obtained.Predecessor is put into tube furnace, in inert gas
1050 DEG C are warming up to 5 DEG C/min rate under argon gas protection, and heat preservation 3h is pyrolyzed, and is cooled to the furnace after room temperature to sieve and is obtained
Si-Fe/C/CNTs composite material.
Comparative example 1
The Si-Fe alloy for being 56 μm by average particle size that CN108346788A is used makes button cell.
Comparative example 2
What CN108346788A was used weighs the Si-Fe alloy that 60g average particle size is 56 μm, the mixing of 18g pitch, wherein
Asphalt quality is the 23% of amount of the mixture, predecessor is placed in tube furnace, under protection of argon gas, with 5 DEG C/min rate liter
Temperature keeps the temperature 3h, cools to room temperature with the furnace to 1050 DEG C；Grinding, screening, obtain Si-Fe/C composite material.
Comparative example 3
What CN108346788A was used weighs the Si-Fe alloy that 15g average particle size is 56 μm, and 30mL dehydrated alcohol is added,
It is placed in high energy ball mill, setting speed 400rpm, Ball-milling Time 5h.It is put into vacuum oven, 80 DEG C of dry 12h are obtained
The Si-Fe alloyed powder that average particle size is 3 μm makes button cell.
Experimental example 1
The composite negative pole material being prepared using 1~embodiment of embodiment 17 makes button cell, using comparative example 1~
The negative electrode material that comparative example 3 is prepared makes button cell.And electrochemical property test is carried out, the result of test such as following table institute
Show:
The chemical property of the negative electrode material of 1 embodiment and comparative example of table
Si-Fe and Si-Fe/C composite negative pole material made from above-described embodiment 1~17 and comparative example 1~3 is fabricated to
2032 type button simulated batteries test its chemical property.Specific step is as follows: (1) negative electrode material, conductive acetylene is black and viscous
Agent (sodium carboxymethylcellulose and butadiene-styrene rubber mixture, mass ratio 3:5) 80:10:10 in mass ratio mixing is tied, with deionized water
For solvent, stirs evenly and slurry is made；(2) wet electrode is put into vacuum oven on copper foil matrix by slurry even application
It is interior, 80 DEG C of dry 12h；(3) in dry vacuum glove box, simulated battery is assembled.It is anode, metal with above-mentioned self-made electrode
Lithium piece is cathode, and Celgard2500 film is diaphragm, the LiPF of 1mol/L6It is dissolved in ethylene carbonate (EC), methyl ethyl ester
(EMC) and the solution of dimethyl carbonate (DMC) (volume ratio 1:1:1) is electrolyte.
By data shown in table 1 it is found that based on modified lithium-ion electric provided by preferred embodiment of the invention
The electrochemical performance for the composite material that the preparation method of pond silicon-base alloy composite negative pole material is prepared.Wherein, specifically
Ground is to be modified the electrification that can effectively improve material to Si-Fe alloy using ball milling, carbon coating, the means of doping conductive agent
Learn performance.The chemical property of negative electrode material provided by comparative example 1~3 need to be improved.
In conclusion prepared by the preparation method of the silicon-based composite anode material for Li-ion battery of preferred embodiments of the present invention
Obtain the electrochemical performance of composite negative pole material.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of preparation method based on modified lithium ion battery silicon-base alloy composite negative pole material, which is characterized in that it is wrapped
It includes:
Si-Fe alloy is modified to obtain Si-Fe/ using one of ball milling, carbon coating, doping conductive agent or various ways
Pitch predecessor, Si-Fe/SBR predecessor, Si-Fe/ pitch/CNTs predecessor, in Si-Fe/ pitch/graphene predecessor
Any modified product；
The modified product is put in tube furnace, preset temperature is warming up to scheduled rate under inert gas argon gas shielded
Afterwards, heat preservation preset time is pyrolyzed, and cools to room temperature with the furnace, the lithium ion battery silicon-base alloy Compound Negative is obtained after screening
Pole material.
2. the preparation method according to claim 1 based on modified lithium ion battery silicon-base alloy composite negative pole material,
It is characterized in that, the preparation of the Si-Fe/ pitch predecessor specifically includes:
The ferro-silicon alloy powder that 14~50g average grain diameter is 56 μm is weighed, addition 150mL deionized water, which is placed in ball mill, to be carried out
Ball milling obtains the Antaciron slurry that mean particle size is 0.58~7.7 μm；Wherein, ball milling is placed in stirring ball mill
It carries out, and is the zirconium ball for using diameter as 0.3~1.2mm of φ, ratio of grinding media to material 20:1, the ball milling 1h at 2500rpm；
The Antaciron slurry after ball milling is put into vacuum oven and in 120 DEG C of at a temperature of dry 12h；
The pitch of addition 30% is mixed on batch mixer with 100rpm after the ferro-silicon alloy powder after drying is ground up, sieved
12h obtains the Si-Fe/ pitch predecessor.
3. the preparation method according to claim 2 based on modified lithium ion battery silicon-base alloy composite negative pole material,
It is characterized in that, the preparation of the Si-Fe/ pitch predecessor also specifically includes:
After 14~50g average grain diameter is that the citric acid of 5g is added in 56 μm of the ferro-silicon alloy powder, add 150mL go from
Sub- water, which is placed in ball mill, carries out ball milling, obtains the Antaciron slurry that mean particle size is 0.23~1.0 μm.
4. the preparation method according to claim 1 based on modified lithium ion battery silicon-base alloy composite negative pole material,
It is characterized in that, the preparation of the Si-Fe/ pitch predecessor also specifically includes:
After weighing ferro-silicon alloy powder, the citric acid of 5g and the pitch of 15g that 14~50g average grain diameter is 56 μm, 150mL is added
Deionized water, which is placed in ball mill, carries out ball milling, obtains Si-Fe/ pitch predecessor slurry；Wherein, ball milling is placed in stirring-type ball
It is carried out in grinding machine, and is the zirconium ball for using diameter as 0.3~1.2mm of φ, ratio of grinding media to material 20:1, the ball milling 1h at 2500rpm；
The Si-Fe/ pitch predecessor slurry is put into vacuum oven at 120 DEG C, dry 12h after being ground up, sieved, obtains institute
State Si-Fe/ pitch predecessor.
5. the preparation method according to claim 1 based on modified lithium ion battery silicon-base alloy composite negative pole material,
It is characterized in that, the preparation of the Si-Fe/ pitch predecessor specifically includes:
The ferro-silicon alloy powder that 14~50g average grain diameter is 56 μm is weighed, the alcohol that 60mL is added, which is placed in ball mill, carries out ball
Mill, obtains Si-Fe slurry；Wherein, ball milling is placed in carries out in planetary ball mill, and is use diameter for φ 5mm and φ 3mm
Each 50% tungsten-carbide ball, ratio of grinding media to material 20:1, the ball milling 5h at 400rpm；
The pitch of 12g is added after the Si-Fe slurry to be added to the deionized water dilution of 1000mL, and is carried out in spraying machine
It is dry, and 300 DEG C of inlet temperature, 100 DEG C of outlet temperature, obtain the Si-Fe/ pitch predecessor.
6. the preparation method according to claim 1 based on modified lithium ion battery silicon-base alloy composite negative pole material,
It is characterized in that, the preparation of the Si-Fe/SBR predecessor specifically includes:
The ferro-silicon alloy powder that 14~50g average grain diameter is 56 μm is weighed, the alcohol that 60mL is added, which is placed in ball mill, carries out ball
Mill, obtains Si-Fe slurry；Wherein, ball milling is placed in carries out in planetary ball mill, and is use diameter for φ 5mm and φ 3mm
Each 50% tungsten-carbide ball, ratio of grinding media to material 20:1, the ball milling 5h at 400rpm；
The butadiene-styrene rubber of 12g is added after the deionized water that 1000mL is added in the Si-Fe slurry is diluted, and in spraying machine
It is dried, and 300 DEG C of inlet temperature, 100 DEG C of outlet temperature, obtains the Si-Fe/SBR predecessor.
7. the preparation method according to claim 1 based on modified lithium ion battery silicon-base alloy composite negative pole material,
It is characterized in that, the preparation of the Si-Fe/ pitch/CNTs predecessor specifically includes:
The ferro-silicon alloy powder that 14~50g average grain diameter is 56 μm is weighed, the alcohol that 60mL is added, which is placed in ball mill, carries out ball
Mill, obtains Si-Fe slurry；Wherein, ball milling is placed in carries out in planetary ball mill, and is use diameter for φ 5mm and φ 3mm
Each 50% tungsten-carbide ball, ratio of grinding media to material 20:1, the ball milling 5h at 400rpm；
The pitch of 12g and 4% carbon nanotube are added after the Si-Fe slurry to be added to the deionized water dilution of 1000mL,
After being stirred under vacuum 1h, it is dried in spraying machine, and 300 DEG C of inlet temperature, 100 DEG C of outlet temperature, obtains the Si-Fe/
Pitch/CNTs predecessor.
8. the preparation method according to claim 1 based on modified lithium ion battery silicon-base alloy composite negative pole material,
It is characterized in that, the preparation of the Si-Fe/ pitch/graphene predecessor specifically includes:
The ferro-silicon alloy powder that 14~50g average grain diameter is 56 μm is weighed, 2%~10% graphene and the alcohol of 30mL is added
It is placed in ball mill and carries out ball milling, obtain Si-Fe/ pitch/graphene slurry；Wherein, ball milling is placed in planetary ball mill
It carries out, and is each 50% tungsten-carbide ball for using diameter as φ 5mm and φ 3mm, ratio of grinding media to material 20:1, the ball milling at 400rpm
5h；
Si-Fe/ pitch/graphene the slurry is put into vacuum oven, and 80 DEG C at a temperature of dry 12h after obtain
Si-Fe/ pitch/graphene the predecessor.
9. the preparation method according to claim 1 based on modified lithium ion battery silicon-base alloy composite negative pole material,
It is characterized by:
It prepares the lithium ion battery silicon-base alloy composite negative pole material using the Si-Fe/ pitch predecessor to specifically include: will
The Si-Fe/ pitch predecessor is put in tube furnace, is warming up to 850 under inert gas argon gas shielded with 5 DEG C/min rate
DEG C, heat preservation 3h is pyrolyzed, and screening obtains Si-Fe/C composite material after cooling to room temperature with the furnace；
It using the Si-Fe/SBR predecessor, prepares the lithium ion battery silicon-base alloy composite negative pole material and specifically includes: will
The Si-Fe/SBR predecessor is put in tube furnace, is warming up to 850 DEG C under inert gas argon gas shielded with 5 DEG C/min rate,
Heat preservation 3h is pyrolyzed, and screening obtains Si-Fe/C composite material after cooling to room temperature with the furnace；
The lithium ion battery silicon-base alloy composite negative pole material is prepared using the Si-Fe/ pitch/CNTs predecessor specifically to wrap
It includes: the Si-Fe/ pitch/CNTs predecessor being put in tube furnace, with 5 DEG C/min rate under inert gas argon gas shielded
850 DEG C~1050 DEG C are warming up to, heat preservation 3h is pyrolyzed, and screening obtains Si-Fe/C/CNTs composite wood after cooling to room temperature with the furnace
Material；
It is specific that the lithium ion battery silicon-base alloy composite negative pole material is prepared using the Si-Fe/ pitch/graphene predecessor
It include: that the Si-Fe/ pitch/graphene predecessor is put in tube furnace, with 5 DEG C/min under inert gas argon gas shielded
Rate is warming up to 850 DEG C~1050 DEG C, and heat preservation 3h is pyrolyzed, and screening obtains Si-Fe/C/ graphene after cooling to room temperature with the furnace
Composite material.
10. a kind of lithium ion battery silicon-base alloy composite negative pole material, which is characterized in that the lithium ion battery silicon-base alloy is multiple
Negative electrode material is closed to pass through described in any one of claims 1 to 9 based on modified lithium ion battery silicon-base alloy composite negative pole
The preparation method of material is prepared.
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Application publication date: 20190312 Assignee: Guangzhou shunyao Energy Technology Co.,Ltd. Assignor: Institute of resource utilization and rare earth development, Guangdong Academy of Sciences Contract record no.: X2024980006118 Denomination of invention: A preparation method of modified silicon-based alloy composite negative electrode material for lithium-ion batteries Granted publication date: 20210105 License type: Common License Record date: 20240523 |