CN109873146A - A kind of lithium-ion battery silicon-carbon anode material and preparation method thereof - Google Patents
A kind of lithium-ion battery silicon-carbon anode material and preparation method thereof Download PDFInfo
- Publication number
- CN109873146A CN109873146A CN201910147019.1A CN201910147019A CN109873146A CN 109873146 A CN109873146 A CN 109873146A CN 201910147019 A CN201910147019 A CN 201910147019A CN 109873146 A CN109873146 A CN 109873146A
- Authority
- CN
- China
- Prior art keywords
- silicon
- lithium
- ion battery
- preparation
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of lithium-ion battery silicon-carbon anode material and preparation method thereof, comprising the following steps: step 1, in a solvent by micron silicon dispersion, dispersing agent and conductive agent is added, grinding forms pre-oxidation nano-silicon slurries；Step 2, organic carbon source is dissolved in solvent, adds the pre-oxidation nano-silicon slurries that step 1 obtains, is then dried to obtain presoma 1；Step 3, presoma 1 is carbonized to obtain presoma 2 in protective atmosphere high temperature；Step 4, secondary carbon coating is carried out to presoma 2 by the way of gas phase cladding to get the silicon-carbon composite cathode material is arrived.The present invention solves the problems, such as that outer layer carbon coating layer is uneven, unsound, has completely cut off contact of the silicon with electrolyte, has reduced side reaction, so that cycle performance of battery is promoted.
Description
Technical field
The invention belongs to lithium ion battery negative material field, be related to a kind of lithium-ion battery silicon-carbon anode material and its
Preparation method.
Background technique
Currently, the lithium ion battery of commodity generally makees negative electrode material using graphite carbon material, such as artificial graphite, natural stone
Ink, carbonaceous mesophase spherules, soft carbon, hard carbon etc..But such carbon material specific discharge capacity is lower, and high-rate charge-discharge capability is poor,
And the space for further increasing its specific capacity is smaller, develops far from the following high capacity of enough satisfactions, extended-life lithium ion battery
Requirement.Therefore, it is necessary to a kind of materials of height ratio capacity, and graphite type material to be replaced to do negative electrode material.In numerous negative electrode materials,
Silicium cathode has the theoretical specific capacity (4200mAh/g) much higher than graphite cathode, there is slightly above graphite cathode voltage platform,
Make that lithium will not be analysed when its charging, there is good security performance, become the most potential material instead of graphite cathode.But it is being filled
Serious volume change occurs for discharge process, and active material is caused to separate with collector, collector is removed, under battery capacity is rapid
Drop.Meanwhile huge volume change makes solid electrolyte film (SEI) constantly rupture and be formed, and constantly consumes anode and deposits
Lithium, battery capacity constantly reduce, and cycle performance is deteriorated.
In order to solve the problems, such as that silicium cathode volume change in charge and discharge process is larger, those skilled in the art pass through silicon
The volume change of the technologies of preparing buffering silicon such as nanosizing, the dispersion cladding of the surface oxidation of silicon, silicon, can be commercialized and answer
With.
107408681 A of patent document CN discloses a kind of silicium cathode active material and preparation method thereof, which also will
Silicon nanosizing, and pre-oxidized, while having coated carbon in outer silicon, it is suppressed that the expansion of silicon, while enhancing silicon particle
Between electric conductivity.But it carries out the secondary cladding of liquid phase with the solution containing organic carbon source, so that outer layer carbon coating layer is uneven,
Meanwhile organic carbon source remaining carbon is low, material specific surface area is larger after thermal decomposition, and nano-silicon is easy to electrolyte contacts, causes to recycle
Performance is poor.
108400307 A of patent document CN discloses a kind of embedded silicon-carbon cathode material of apple shape and preparation method thereof,
The invention binder connects together silicon and graphite, and the buffering matrix for using graphite to expand as silicon reduces the expansion of material.But
It uses binder to coat nano-silicon as organic carbon source, and material specific surface area is larger after organic matter thermal decomposition, and nano-silicon is easy to electricity
Liquid contact is solved, causes cycle performance poor.
Therefore suitable secondary cladding mode is selected, so that outer layer carbon coating layer is uniformly and fine and close, reduces nano-silicon and electricity
The contact of liquid is solved, cycle performance of battery is improved, silicon carbon material commercial applications in lithium battery is realized, is that this field is urgently to be resolved
The problem of.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of lithium-ion battery silicon-carbon anode material and its preparation
Method solves the problems, such as that outer layer carbon coating layer is uneven, unsound, has completely cut off contact of the silicon with electrolyte, reduces secondary anti-
It answers, so that cycle performance of battery is promoted.
The present invention is to be achieved through the following technical solutions:
A kind of preparation method of lithium-ion battery silicon-carbon anode material, comprising the following steps:
Step 1, in a solvent by micron silicon dispersion, dispersing agent and conductive agent is added, grinding forms pre-oxidation nano-silicon slurry
Liquid；
Step 2, organic carbon source is dissolved in solvent, adds the pre-oxidation nano-silicon slurries that step 1 obtains, then does
It is dry to obtain presoma 1；
Step 3, presoma 1 is carbonized to obtain presoma 2 in protective atmosphere high temperature；
Step 4, secondary carbon coating is carried out to presoma 2 by the way of gas phase cladding to get the silicon-carbon Compound Negative is arrived
Pole material.
Preferably, in step 1, dispersing agent is stearic acid, polyvinylpyrrolidone, acid polyethylene, polyvinyl lactam, 12
Sodium alkyl sulfate, cetyl trimethylammonium bromide, oleic acid, polyethylene nitrile, sodium tripolyphosphate, calgon, sodium pyrophosphate
One or more of with amine surfactants；Conductive agent is one of conductive black, graphene and carbon nanotube or several
Kind；In step 1 and step 2, solvent is one or more of alcohols, ketone, alkanes, lipid and tetrahydrofuran.
Preferably, in step 1, micron silicon partial size is 1 μm~10 μm, and nano-silicon partial size is 50~200nm；According to quality hundred
Score meter, pre-oxidizing oxygen content in nano-silicon is 5%~25%.
Preferably, in step 2, organic carbon source is polyvinyl butyral, phenolic resin, epoxy resin, pitch, vinyl chloride
One or more of resin, glucose, citric acid, polyacrylate and ribose.
Preferably, in step 2, dry for spray drying, inlet temperature is 120 DEG C~220 DEG C, outlet temperature is 75 DEG C~
120℃；It is atomized 10000~30000rpm/min of disk rotating speed.
Preferably, in step 3, high temperature cabonization temperature is 700 DEG C~1400 DEG C and keeps the temperature 1h~5h, and protective atmosphere is nitrogen
One or more of gas, argon gas, helium or reducibility gas.
Preferably, in step 4, gas phase coat when cladding gas be alkanes gas, acetylenic gas, acetone, natural gas and
One or more of liquefied petroleum gas.
Preferably, in step 4, gas phase temperature of plate is 500~1100 DEG C, and gas phase coats the time as 1~10h.
Preferably, the mass ratio of micron silicon and organic carbon source are as follows: (200-1000): (40-800).
The lithium-ion battery silicon-carbon anode material that the preparation method is prepared.
Compared with prior art, the invention has the following beneficial technical effects:
The technical effect of preparation method of the present invention includes following several points: (1) by micron silicon nanosizing, nano-silicon is controllably pre-
Oxidation, makes its Surface Creation oxide layer, it is suppressed that volume expansion of the silicon in charge and discharge process reduces granule atomization and activity
Substance falls off, and improves cycle performance of battery；(2) one layer of conductive carbon of nano-silicon particle outer cladding both facilitates the body for inhibiting silicon
Product expansion, and the electric conductivity between silicon particle is increased, improve material electrochemical performance；(3) two are used as using gas phase cladding
The method of secondary cladding, obtained outer layer carbon coating layer is uniformly and fine and close, reduces material specific surface area, has completely cut off silicon and electrolyte
Direct contact, improve cycle performance of battery.
The material that the present invention obtains, outer layer carbon coating layer is uniformly and fine and close, reduces material specific surface area, completely cut off silicon with
The direct contact of electrolyte, improves cycle performance of battery.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) picture that the embodiment of the present invention 1 prepares material.
Fig. 2 is the cycle performance curve that the embodiment of the present invention 1 prepares material.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
The preparation method of lithium-ion battery silicon-carbon anode material of the present invention, comprising the following steps:
Step 1, in a solvent by micron silicon dispersion, dispersing agent and conductive agent is added, grinding forms pre-oxidation nano-silicon slurry
Liquid；
Step 2, organic carbon source is dissolved in solvent；Organic carbon source solution is added in the nano-silicon slurries of above-mentioned pre-oxidation
In, then it is dried to obtain presoma 1；
Step 3, presoma 1 is carbonized to obtain presoma 2 in protective atmosphere high temperature；
Step 4, secondary carbon coating is carried out to presoma 2 by the way of gas phase cladding to get the silicon-carbon Compound Negative is arrived
Pole material.
In step 1, the solvent is organic solvent, selected from one of alcohols, ketone, alkanes, lipid and tetrahydrofuran
Or it is several, the micron silicon partial size is 1 μm~10 μm, and the nano-silicon partial size is 50~200nm；According to mass percentage,
Oxygen content is 5%~25% in the pre-oxidation nano-silicon.
In step 1, dispersing agent is stearic acid, polyvinylpyrrolidone, acid polyethylene, polyvinyl lactam, dodecyl sulphur
Sour sodium, cetyl trimethylammonium bromide, oleic acid, polyethylene nitrile, sodium tripolyphosphate, calgon, sodium pyrophosphate and amine
One of surfactant is a variety of, and inventive dispersant is without being limited thereto；The conductive agent is conductive black, graphene and carbon
One or more of nanotube.
In step 2, organic carbon source is polyvinyl butyral, phenolic resin, epoxy resin, pitch, vinyl chloride resin, Portugal
Grape sugar, citric acid and one or more of polyacrylate and ribose, organic carbon source of the present invention are without being limited thereto.
In step 2, the drying is dry stirring, rotary drying, vacuum drying, freeze-drying or spray drying；It is preferred that
Ground, the drying are spray drying, and inlet temperature is 120 DEG C~220 DEG C, and outlet temperature is 75 DEG C~120 DEG C；It is atomized disk rotating speed
10000~30000rpm/min；
In step 3, high temperature cabonization equipment is any one in tube furnace, batch-type furnace, rotary kiln, roller kilns and pushed bat kiln
Kind, high temperature cabonization temperature is 700 DEG C~1400 DEG C and keeps the temperature 1h~5h, and protective atmosphere is nitrogen, argon gas, helium or reproducibility gas
One or more of body；
In step 4, cladding gas when gas phase coats is alkanes gas, acetylenic gas, acetone, natural gas and liquefied petroleum
One or more of gas；Gas phase temperature of plate is 500~1100 DEG C；Gas phase coats the time as 1~10h.
The mass ratio of micron silicon in step 1 and the organic carbon source in step 2 are as follows: (200-1000): (40-800).
Embodiment of the present invention is described in detail below in conjunction with embodiment.Those skilled in the art will manage
Solution, following embodiment is merely a preferred embodiment of the present invention, and in order to better understand the present invention, thus should not be regarded as limiting this
The range of invention.For those skilled in the art, the invention may be variously modified and varied, all in essence of the invention
Within mind and principle, any modification, equivalent replacement or improvement for being made etc. be should all be included in the protection scope of the present invention.
Embodiment 1
The silicon powder that 300g median particle diameter is 5 μm is distributed in 3000g alcohol solvent, 4.5g stearic acid and 30g are added
Above-mentioned solution is added ball milling 12h in ball mill and obtains the nano-silicon slurries that median particle diameter is 150nm, according to quality by graphene
Percentage meter, oxygen content is 9.5% in nano-silicon；40g phenolic resin is dissolved in 500g ethanol solution, above-mentioned receive then is added
Rice silicon slurries, and 30min is stirred, it is spray-dried later, spray drying parameters are that inlet temperature is 220 DEG C, outlet temperature
It is 75 DEG C, is atomized disk rotating speed 30000rpm/min, obtains presoma 1；Presoma 1 is put into batch-type furnace, in a nitrogen atmosphere
700 DEG C are heated to, heat preservation 1h carries out high temperature cabonization, obtains presoma 2；Presoma is heated to 1000 DEG C, is passed through acetylene gas
Gas phase coats 5h, and cooling, 325 meshes point remove magnetic, obtains the silicon-carbon cathode material.
Embodiment 2
The silicon powder that 200g median particle diameter is 10 μm is distributed in 2500g acetone solvent, 10g polyvinylpyrrolidine is added
Above-mentioned solution is added ball milling 15h in ball mill and obtains the nano-silicon slurries that median particle diameter is 50nm by ketone and 20g carbon nanotube,
According to mass percentage, oxygen content is 13% in nano-silicon；80g polyvinyl butyral is dissolved in 1000g acetone soln,
Then above-mentioned nano-silicon slurries are added, and stir 30min, be spray-dried later, spray drying parameters are inlet temperature
It is 150 DEG C, outlet temperature is 100 DEG C, is atomized disk rotating speed 20000rpm/min, obtains presoma 1；Presoma 1 is put into tubular type
In furnace, it is heated to 1400 DEG C under an argon atmosphere, heat preservation 5h carries out high temperature cabonization, obtains presoma 2；Presoma is heated to
1100 DEG C, it is passed through acetone gas gas phase cladding 10h, cooling 325 meshes are divided, except magnetic obtains the silicon-carbon cathode material.
Embodiment 3
The silicon powder that 250g median particle diameter is 3 μm is distributed in 3000g isopropyl acetate solvent, 15g polyethylene is added
Above-mentioned solution is added ball milling 10h in ball mill and obtains the nano-silicon slurries that median particle diameter is 80nm by acid and 10g conductive black,
According to mass percentage, oxygen content is 5% in nano-silicon；50g citric acid is dissolved in 800g isopropyl acetate solution, then
Above-mentioned nano-silicon slurries are added, and stir 30min, are spray-dried later, spray drying parameters are that inlet temperature is 120
DEG C, outlet temperature is 80 DEG C, is atomized disk rotating speed 25000rpm/min, obtains presoma 1；Presoma 1 is put into pushed bat kiln,
1200 DEG C are heated under hydrogen atmosphere, heat preservation 3h carries out high temperature cabonization, obtains presoma 2；Presoma is heated to 900 DEG C, is led to
Enter methane gas gas phase cladding 1h, cooling 325 meshes are divided, except magnetic obtains the silicon-carbon cathode material.
Embodiment 4
The silicon powder that 550g median particle diameter is 1 μm is distributed in 5000g n-hexane solvent, 35g polyvinyl lactam is added
With 25g conductive black, ball milling 20h in ball mill is added in above-mentioned solution and obtains the nano-silicon slurries that median particle diameter is 100nm, is pressed
According to mass percentage, oxygen content is 25% in nano-silicon；800g glucose is dissolved in 1000g hexane solution, then will
Above-mentioned nano-silicon slurries are added, and stir 30min, are spray-dried later, spray drying parameters are that inlet temperature is 160
DEG C, outlet temperature is 100 DEG C, is atomized disk rotating speed 28000rpm/min, obtains presoma 1；Presoma 1 is put into roller kilns,
It is heated to 900 DEG C in a nitrogen atmosphere, heat preservation 5h carries out high temperature cabonization, obtains presoma 2；Presoma is heated to 800 DEG C, is led to
Enter natural-gas gas phase cladding 4h, cooling 325 meshes are divided, except magnetic obtains the silicon-carbon cathode material.
Embodiment 5
The silicon powder that 1000g median particle diameter is 8 μm is distributed in 10kg tetrahydrofuran solvent, 60g polyethylene nitrile is added
With 60g carbon nanotube, ball milling 16h in ball mill is added in above-mentioned solution and obtains the nano-silicon slurries that median particle diameter is 90nm, is pressed
According to mass percentage, oxygen content is 20% in nano-silicon；120g pitch is dissolved in 1000g tetrahydrofuran solution, then will
Above-mentioned nano-silicon slurries are added, and stir 30min, are spray-dried later, spray drying parameters are that inlet temperature is 180
DEG C, outlet temperature is 120 DEG C, is atomized disk rotating speed 25000rpm/min, obtains presoma 1；Presoma 1 is put into rotary kiln,
1300 DEG C are heated under helium atmosphere, heat preservation 2h carries out high temperature cabonization, obtains presoma 2；Presoma is heated to 500 DEG C,
It is passed through compressed petroleum gas gas phase cladding 8h, cooling 325 meshes are divided, except magnetic obtains the silicon-carbon cathode material.
Embodiment 6
The silicon powder that 400g median particle diameter is 8 μm is distributed to the in the mixed solvent of 2000g ethyl alcohol and acetone, adds 4.5g
Lauryl sodium sulfate and 30g graphene, it is 200nm's that above-mentioned solution, which is added ball milling 10h in ball mill to obtain median particle diameter,
Nano-silicon slurries, according to mass percentage, oxygen content is 8% in nano-silicon；By 100g epoxy resin be dissolved in 500g ethyl alcohol and
Then the in the mixed solvent of acetone is added above-mentioned nano-silicon slurries, and stirs 30min, be spray-dried later, spray drying
Parameter is that inlet temperature is 120 DEG C, and outlet temperature is 80 DEG C, is atomized disk rotating speed 10000rpm/min, obtains presoma 1；Will before
It drives body 1 to be put into batch-type furnace, is heated to 750 DEG C in a nitrogen atmosphere, heat preservation 2h carries out high temperature cabonization, obtains presoma 2；Will before
It drives body and is heated to 800 DEG C, be passed through acetylene gas gas phase cladding 5h, cooling, 325 meshes point remove magnetic, obtain the silicon-carbon cathode material
Material.
Embodiment 7
The silicon powder that 500g median particle diameter is 4 μm is distributed in 1000g methanol solvate, 2.5g oleic acid, 2g trimerization are added
Above-mentioned solution is added ball milling 12h in ball mill and obtains the nano-silicon slurry that median particle diameter is 150nm by sodium phosphate and 30g graphene
Liquid, according to mass percentage, oxygen content is 12% in nano-silicon；200g polyacrylate is dissolved in 1000g methanol solvate,
Then above-mentioned nano-silicon slurries are added, and stir 40min, are spray-dried later, spray drying parameters are that inlet temperature is
200 DEG C, outlet temperature is 90 DEG C, is atomized disk rotating speed 15000rpm/min, obtains presoma 1；Presoma 1 is put into batch-type furnace
In, it is heated to 800 DEG C in a nitrogen atmosphere, heat preservation 1h carries out high temperature cabonization, obtains presoma 2；Presoma is heated to 900
DEG C, it is passed through acetylene gas gas phase cladding 3h, cooling, 325 meshes point remove magnetic, obtain the silicon-carbon cathode material.
Embodiment 8
The silicon powder that 600g median particle diameter is 6 μm is distributed in 3000g alcohol solvent, 7g cetyl trimethyl is added
Above-mentioned solution is added ball milling 12h in ball mill and obtains median particle diameter by the mixture of ammonium bromide and 60g graphene and carbon nanotube
For the nano-silicon slurries of 100nm, according to mass percentage, oxygen content is 20% in nano-silicon；By 300g vinyl chloride resin and
The mixture of ribose is dissolved in 1500g ethanol solution, above-mentioned nano-silicon slurries is then added, and stir 30min, is sprayed later
Mist is dry, and spray drying parameters are that inlet temperature is 200 DEG C, and outlet temperature is 100 DEG C, is atomized disk rotating speed 20000rpm/min,
Obtain presoma 1；Presoma 1 is put into batch-type furnace, is heated to 1100 DEG C in a nitrogen atmosphere, heat preservation 1h carries out pyrocarbon
Change, obtains presoma 2；Presoma is heated to 1100 DEG C, is passed through the mixed gas gas phase cladding 5h of acetylene and butane, cool down,
325 meshes point remove magnetic, obtain the silicon-carbon cathode material.
Embodiment 9
The silicon powder that 350g median particle diameter is 5 μm is distributed in 3000g alcohol solvent, 5g sodium pyrophosphate and 35g are added
Above-mentioned solution is added ball milling 12h in ball mill and obtains the nano-silicon slurries that median particle diameter is 100nm, according to quality by graphene
Percentage meter, oxygen content is 22% in nano-silicon；The mixture of 700g epoxy resin and glucose is dissolved in 2000g ethanol solution
In, above-mentioned nano-silicon slurries are then added, and stir 30min, are spray-dried later, spray drying parameters are inlet temperature
It is 220 DEG C, outlet temperature is 75 DEG C, is atomized disk rotating speed 10000rpm/min, obtains presoma 1；Presoma 1 is put into batch-type furnace
In, it is heated to 700 DEG C in a nitrogen atmosphere, heat preservation 1h carries out high temperature cabonization, obtains presoma 2；Presoma is heated to 700
DEG C, it is passed through acetylene and acetone mixed gas gas phase cladding 5h, cooling, 325 meshes point remove magnetic, obtain the silicon-carbon cathode material.
Examples 1 to 5 sample is tested using following test method:
Using the 3020 ratio surface area instrument test material of Micromeritics TriStar II of Micromeritics Instrument Corp. U.S.A
Specific surface area.
Using Malvern laser particle analyzer MS2000 test material average grain diameter.
Using scanning electron microscope test material surface pattern etc..
It can oxygen nitrogen hydrogen analyzer analysis nano-silicon weight oxygen content using LECO power.
1~5 gained sample of above-described embodiment and graphite are arranged in pairs or groups, assemble full battery, full battery by specific capacity 420mAh/g
Assembling test method is as follows: by negative electrode material, conductive agent and binder, 93:1.5:5.5 is mixed in a solvent by mass percentage,
Controlling slurry solid content is 48%, is coated onto 8 μm of copper foil current collector, is dried, and cutting obtains cathode pole piece；Then it takes
LiPF6/EC+DMC+EMC (V/V=1:1:1) electrolyte, Celgard2400 diaphragm with tertiary cathode pole piece, 1mol/L, group
Dress up the soft-package battery of capacity 2.4Ah.It is tested using Wuhan Jin Nuo Electronics Co., Ltd. LAND battery test system room temperature, test
Condition: 0.2C constant current charge-discharge, charging/discharging voltage are limited in 2.75~4.2V.
Test result is as shown in table 1, it can be seen that material specific surface area of the present invention is smaller, illustrates that outer layer carbon coating is equal
Even densification has completely cut off silicon and has contacted with the direct of electrolyte, so that the cycle performance of material is preferable, capacity retention ratio exists within 300 weeks
90% or more.
1 negative electrode material chemical property transitivity test result of table
The SEM figure of material prepared by embodiment 1 is as shown in Figure 1, it can be seen that and material surface does not have nano-silicon to expose,
That is the complete cladding of the achievable nano-silicon of the present invention, reduces material specific surface area, and silicon and the direct of electrolyte is avoided to connect
Touching.Simultaneously, it can be seen that recess occurs in material granule surface prepared by the present invention, has reserved expansion space outside, has helped
It is influenced caused by particle expansion in reducing, this is because the dispersing agent used also functions to the effect of binder in spray process,
Under binder effect, caused by solvent evaporation is uneven in spray-drying process.
Embodiment 1 prepare material cycle performance curve as shown in Fig. 2, the material have excellent cycle performance, 300
All capacity retention ratios are 90%.
The present invention pre-oxidizes nano-silicon, effectively reduces the volume change that silicon is crossed in charge and discharge in layer.Meanwhile it will be to
Dispersing agent, conductive agent, organic carbon source are added in nano-silicon slurries and carries out mist projection granulating, makes one layer of nano-silicon coated with uniform to lead
Electrical carbon later coats second particle, reduces the exposed nano-silicon of composite material surface, and specific surface area reduces, and reduces silicon
Contact with electrolyte greatly improves the cycle performance of battery.
Claims (10)
1. a kind of preparation method of lithium-ion battery silicon-carbon anode material, which comprises the following steps:
Step 1, in a solvent by micron silicon dispersion, dispersing agent and conductive agent is added, grinding forms pre-oxidation nano-silicon slurries；
Step 2, organic carbon source is dissolved in solvent, adds the pre-oxidation nano-silicon slurries that step 1 obtains, it is then dry
To presoma 1；
Step 3, presoma 1 is carbonized to obtain presoma 2 in protective atmosphere high temperature；
Step 4, secondary carbon coating is carried out to presoma 2 by the way of gas phase cladding to get the silicon-carbon composite cathode material is arrived
Material.
2. the preparation method of lithium-ion battery silicon-carbon anode material according to claim 1, which is characterized in that step 1
In, dispersing agent is stearic acid, polyvinylpyrrolidone, acid polyethylene, polyvinyl lactam, lauryl sodium sulfate, cetyl
In trimethylammonium bromide, oleic acid, polyethylene nitrile, sodium tripolyphosphate, calgon, sodium pyrophosphate and amine surfactants
It is one or more of；Conductive agent is one or more of conductive black, graphene and carbon nanotube；It is molten in step 1 and step 2
Agent is one or more of alcohols, ketone, alkanes, lipid and tetrahydrofuran.
3. the preparation method of lithium-ion battery silicon-carbon anode material according to claim 1, which is characterized in that step 1
In, micron silicon partial size is 1 μm~10 μm, and nano-silicon partial size is 50~200nm；According to mass percentage, nano-silicon is pre-oxidized
Middle oxygen content is 5%~25%.
4. the preparation method of lithium-ion battery silicon-carbon anode material according to claim 1, which is characterized in that step 2
In, organic carbon source be polyvinyl butyral, phenolic resin, epoxy resin, pitch, vinyl chloride resin, glucose, citric acid,
One or more of polyacrylate and ribose.
5. the preparation method of lithium-ion battery silicon-carbon anode material according to claim 1, which is characterized in that step 2
In, dry to be spray-dried, inlet temperature is 120 DEG C~220 DEG C, and outlet temperature is 75 DEG C~120 DEG C；It is atomized disk rotating speed
10000~30000rpm/min.
6. the preparation method of lithium-ion battery silicon-carbon anode material according to claim 1, which is characterized in that step 3
In, high temperature cabonization temperature is 700 DEG C~1400 DEG C and keeps the temperature 1h~5h, and protective atmosphere is nitrogen, argon gas, helium or reproducibility gas
One or more of body.
7. the preparation method of lithium-ion battery silicon-carbon anode material according to claim 1, which is characterized in that step 4
In, cladding gas when gas phase coats be one of alkanes gas, acetylenic gas, acetone, natural gas and liquefied petroleum gas or
It is several.
8. the preparation method of lithium-ion battery silicon-carbon anode material according to claim 1, which is characterized in that step 4
In, gas phase temperature of plate is 500~1100 DEG C, and gas phase coats the time as 1~10h.
9. the preparation method of lithium-ion battery silicon-carbon anode material according to claim 1, which is characterized in that micron silicon
With the mass ratio of organic carbon source are as follows: (200~1000): (40~800).
10. the lithium-ion battery silicon-carbon anode material that the described in any item preparation methods of claim 1-9 are prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910147019.1A CN109873146A (en) | 2019-02-27 | 2019-02-27 | A kind of lithium-ion battery silicon-carbon anode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910147019.1A CN109873146A (en) | 2019-02-27 | 2019-02-27 | A kind of lithium-ion battery silicon-carbon anode material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109873146A true CN109873146A (en) | 2019-06-11 |
Family
ID=66919391
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910147019.1A Pending CN109873146A (en) | 2019-02-27 | 2019-02-27 | A kind of lithium-ion battery silicon-carbon anode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109873146A (en) |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110350161A (en) * | 2019-06-18 | 2019-10-18 | 长沙矿冶研究院有限责任公司 | A kind of preparation method of silicon-carbon cathode presoma |
| CN110504430A (en) * | 2019-08-28 | 2019-11-26 | 陕西煤业化工技术研究院有限责任公司 | A kind of lithium ion battery silicon-carbon cathode material and preparation method thereof |
| CN110854368A (en) * | 2019-11-21 | 2020-02-28 | 陕西煤业化工技术研究院有限责任公司 | High-capacity silicon-carbon negative electrode precursor material and preparation method thereof |
| CN111180713A (en) * | 2020-02-10 | 2020-05-19 | 马鞍山科达普锐能源科技有限公司 | Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof |
| CN111755684A (en) * | 2020-07-06 | 2020-10-09 | 马鞍山科达普锐能源科技有限公司 | Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof |
| CN111755680A (en) * | 2020-07-06 | 2020-10-09 | 马鞍山科达普锐能源科技有限公司 | Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof |
| CN111755677A (en) * | 2020-07-06 | 2020-10-09 | 马鞍山科达普锐能源科技有限公司 | Core-shell structure porous silicon negative electrode material for lithium ion battery and preparation method thereof |
| CN111755678A (en) * | 2020-07-06 | 2020-10-09 | 马鞍山科达普锐能源科技有限公司 | Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof |
| CN112652740A (en) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | Electrode material composition and preparation method and application thereof |
| CN112652742A (en) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | Silicon-carbon composite material and preparation method and application thereof |
| CN112661132A (en) * | 2020-12-23 | 2021-04-16 | 陕西煤业化工技术研究院有限责任公司 | Silicon-based composite negative electrode material and preparation method thereof |
| CN112687861A (en) * | 2020-12-28 | 2021-04-20 | 华中科技大学 | Silicon oxide and preparation method and application thereof |
| CN113363479A (en) * | 2021-03-31 | 2021-09-07 | 万向一二三股份公司 | Double-layer carbon-coated silicon oxide negative electrode material and preparation method and application thereof |
| WO2021208968A1 (en) * | 2020-04-14 | 2021-10-21 | 陕西煤业化工技术研究院有限责任公司 | High-compaction silicon-carbon negative electrode precursor material, preparation method therefor, and high compaction silicon-carbon negative electrode material prepared therefrom |
| CN113644252A (en) * | 2021-08-04 | 2021-11-12 | 西北工业大学 | Silicon-carbon negative electrode material and preparation method thereof |
| CN114566637A (en) * | 2022-02-08 | 2022-05-31 | 泾河新城陕煤技术研究院新能源材料有限公司 | Preparation method of heteroatom doped silicon-carbon negative electrode material and material thereof |
| CN114914407A (en) * | 2021-02-08 | 2022-08-16 | 中国石油化工股份有限公司 | Silicon-carbon composite material and preparation method and application thereof |
| CN115714177A (en) * | 2022-11-14 | 2023-02-24 | 晖阳(贵州)新能源材料有限公司 | Silicon-carbon composite material and preparation method thereof |
| CN115818648A (en) * | 2022-12-30 | 2023-03-21 | 赣州立探新能源科技有限公司 | Silicon-carbon composite material and preparation method and application thereof |
| CN117117159A (en) * | 2023-10-24 | 2023-11-24 | 琥崧智能装备(太仓)有限公司 | Silicon-carbon negative electrode material and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102244240A (en) * | 2011-06-15 | 2011-11-16 | 中南大学 | Lithium ion battery composite anode material and preparation method thereof |
| CN103094533A (en) * | 2012-11-26 | 2013-05-08 | 中南大学 | Multi-core core-shell-structure silicon carbon composite negative pole material and preparation method thereof |
| CN103367727A (en) * | 2013-07-12 | 2013-10-23 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery silicon-carbon anode material and preparation method thereof |
| CN103682266A (en) * | 2013-09-27 | 2014-03-26 | 广州有色金属研究院 | Li and Mn codoped manganese phosphate/carbon composite material and preparation method thereof |
| CN106025219A (en) * | 2016-06-24 | 2016-10-12 | 中天储能科技有限公司 | Spherical silicon-oxygen-carbon negative electrode composite material and preparation method and application thereof |
| CN106532013A (en) * | 2016-12-26 | 2017-03-22 | 贝特瑞（天津）纳米材料制造有限公司 | Lithium iron phosphate/carbon composite material for power battery, and preparation method and application of lithium iron phosphate/carbon composite material |
| CN107799728A (en) * | 2016-08-29 | 2018-03-13 | 南京安普瑞斯有限公司 | A kind of hollow Si-C composite material for lithium ion battery and preparation method thereof |
| US20180166684A1 (en) * | 2012-08-06 | 2018-06-14 | Ut-Battelle, Llc | High capacity monolithic composite si/carbon fiber electrode architectures synthesized from low cost materials and process technologies |
| CN108807861A (en) * | 2017-05-03 | 2018-11-13 | 安普瑞斯（南京）有限公司 | A kind of Si-C composite material and preparation method thereof for lithium ion battery |
-
2019
- 2019-02-27 CN CN201910147019.1A patent/CN109873146A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102244240A (en) * | 2011-06-15 | 2011-11-16 | 中南大学 | Lithium ion battery composite anode material and preparation method thereof |
| US20180166684A1 (en) * | 2012-08-06 | 2018-06-14 | Ut-Battelle, Llc | High capacity monolithic composite si/carbon fiber electrode architectures synthesized from low cost materials and process technologies |
| CN103094533A (en) * | 2012-11-26 | 2013-05-08 | 中南大学 | Multi-core core-shell-structure silicon carbon composite negative pole material and preparation method thereof |
| CN103367727A (en) * | 2013-07-12 | 2013-10-23 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery silicon-carbon anode material and preparation method thereof |
| CN103682266A (en) * | 2013-09-27 | 2014-03-26 | 广州有色金属研究院 | Li and Mn codoped manganese phosphate/carbon composite material and preparation method thereof |
| CN106025219A (en) * | 2016-06-24 | 2016-10-12 | 中天储能科技有限公司 | Spherical silicon-oxygen-carbon negative electrode composite material and preparation method and application thereof |
| CN107799728A (en) * | 2016-08-29 | 2018-03-13 | 南京安普瑞斯有限公司 | A kind of hollow Si-C composite material for lithium ion battery and preparation method thereof |
| CN106532013A (en) * | 2016-12-26 | 2017-03-22 | 贝特瑞（天津）纳米材料制造有限公司 | Lithium iron phosphate/carbon composite material for power battery, and preparation method and application of lithium iron phosphate/carbon composite material |
| CN108807861A (en) * | 2017-05-03 | 2018-11-13 | 安普瑞斯（南京）有限公司 | A kind of Si-C composite material and preparation method thereof for lithium ion battery |
Cited By (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110350161A (en) * | 2019-06-18 | 2019-10-18 | 长沙矿冶研究院有限责任公司 | A kind of preparation method of silicon-carbon cathode presoma |
| CN110504430A (en) * | 2019-08-28 | 2019-11-26 | 陕西煤业化工技术研究院有限责任公司 | A kind of lithium ion battery silicon-carbon cathode material and preparation method thereof |
| CN112652740B (en) * | 2019-10-10 | 2022-10-21 | 中国石油化工股份有限公司 | Electrode material composition and preparation method and application thereof |
| CN112652742B (en) * | 2019-10-10 | 2022-07-12 | 中国石油化工股份有限公司 | Silicon-carbon composite material and preparation method and application thereof |
| CN112652740A (en) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | Electrode material composition and preparation method and application thereof |
| CN112652742A (en) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | Silicon-carbon composite material and preparation method and application thereof |
| CN110854368A (en) * | 2019-11-21 | 2020-02-28 | 陕西煤业化工技术研究院有限责任公司 | High-capacity silicon-carbon negative electrode precursor material and preparation method thereof |
| CN111180713A (en) * | 2020-02-10 | 2020-05-19 | 马鞍山科达普锐能源科技有限公司 | Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof |
| WO2021208968A1 (en) * | 2020-04-14 | 2021-10-21 | 陕西煤业化工技术研究院有限责任公司 | High-compaction silicon-carbon negative electrode precursor material, preparation method therefor, and high compaction silicon-carbon negative electrode material prepared therefrom |
| JP2023522643A (en) * | 2020-04-14 | 2023-05-31 | シャンシー コール ケミカル インダストリー テクノロジー リサーチ インスティテュート カンパニー リミテッド | High-density silicon-carbon anode precursor material, manufacturing method thereof, and manufactured high-density silicon-carbon anode material |
| JP7524344B2 (en) | 2020-04-14 | 2024-07-29 | シャンシー コール ケミカル インダストリー テクノロジー リサーチ インスティテュート カンパニー リミテッド | Silicon carbon anode precursor material and silicon carbon anode material |
| CN111755680A (en) * | 2020-07-06 | 2020-10-09 | 马鞍山科达普锐能源科技有限公司 | Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof |
| CN111755678A (en) * | 2020-07-06 | 2020-10-09 | 马鞍山科达普锐能源科技有限公司 | Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof |
| CN111755677A (en) * | 2020-07-06 | 2020-10-09 | 马鞍山科达普锐能源科技有限公司 | Core-shell structure porous silicon negative electrode material for lithium ion battery and preparation method thereof |
| CN111755684A (en) * | 2020-07-06 | 2020-10-09 | 马鞍山科达普锐能源科技有限公司 | Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof |
| CN112661132A (en) * | 2020-12-23 | 2021-04-16 | 陕西煤业化工技术研究院有限责任公司 | Silicon-based composite negative electrode material and preparation method thereof |
| CN112661132B (en) * | 2020-12-23 | 2023-05-09 | 陕西煤业化工技术研究院有限责任公司 | Silicon-based composite anode material and preparation method thereof |
| CN112687861A (en) * | 2020-12-28 | 2021-04-20 | 华中科技大学 | Silicon oxide and preparation method and application thereof |
| CN112687861B (en) * | 2020-12-28 | 2023-03-10 | 华中科技大学 | Silicon oxide and preparation method and application thereof |
| CN114914407A (en) * | 2021-02-08 | 2022-08-16 | 中国石油化工股份有限公司 | Silicon-carbon composite material and preparation method and application thereof |
| CN113363479A (en) * | 2021-03-31 | 2021-09-07 | 万向一二三股份公司 | Double-layer carbon-coated silicon oxide negative electrode material and preparation method and application thereof |
| CN113644252A (en) * | 2021-08-04 | 2021-11-12 | 西北工业大学 | Silicon-carbon negative electrode material and preparation method thereof |
| CN113644252B (en) * | 2021-08-04 | 2024-06-14 | 西北工业大学 | Silicon-carbon negative electrode material and preparation method thereof |
| CN114566637B (en) * | 2022-02-08 | 2024-02-02 | 泾河新城陕煤技术研究院新能源材料有限公司 | Preparation method of heteroatom doped silicon-carbon anode material and material thereof |
| CN114566637A (en) * | 2022-02-08 | 2022-05-31 | 泾河新城陕煤技术研究院新能源材料有限公司 | Preparation method of heteroatom doped silicon-carbon negative electrode material and material thereof |
| CN115714177A (en) * | 2022-11-14 | 2023-02-24 | 晖阳(贵州)新能源材料有限公司 | Silicon-carbon composite material and preparation method thereof |
| CN115818648A (en) * | 2022-12-30 | 2023-03-21 | 赣州立探新能源科技有限公司 | Silicon-carbon composite material and preparation method and application thereof |
| CN115818648B (en) * | 2022-12-30 | 2024-04-05 | 赣州立探新能源科技有限公司 | Silicon-carbon composite material and preparation method and application thereof |
| CN117117159A (en) * | 2023-10-24 | 2023-11-24 | 琥崧智能装备(太仓)有限公司 | Silicon-carbon negative electrode material and preparation method and application thereof |
| CN117117159B (en) * | 2023-10-24 | 2023-12-26 | 琥崧智能装备(太仓)有限公司 | Silicon-carbon negative electrode material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109873146A (en) | A kind of lithium-ion battery silicon-carbon anode material and preparation method thereof | |
| CN106784640B (en) | Silicon-based composite negative electrode material for lithium ion battery, preparation method of silicon-based composite negative electrode material and lithium ion battery negative electrode containing silicon-based composite negative electrode material | |
| CN108336342B (en) | Si/SiOx/C composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN103708437B (en) | Soft carbon negative material of lithium ion battery, preparation method of soft carbon negative material and lithium ion battery | |
| CN107403919B (en) | Composite material of nitrogen-doped carbon material coated with silicon monoxide and preparation method thereof | |
| CN105742599B (en) | Si-C composite material and preparation method thereof and negative electrode material and battery | |
| CN109755517A (en) | A kind of silicon-carbon composite anode material for lithium ion battery and preparation method thereof | |
| CN103855364A (en) | SiOx-based composite material, preparation method and lithium ion battery | |
| CN108281634A (en) | A kind of method and its application of graphene coated graphite negative material of lithium ion battery | |
| CN103094552A (en) | Surface coating method of 5V lithium ion battery positive pole material LiNi0.5-xMn1.5MxO4 | |
| CN107204431B (en) | Lithium ion battery negative electrode active material, preparation method thereof, negative electrode containing negative electrode active material and battery | |
| CN102790204B (en) | Preparation method of silicon carbon lithium ion battery cathode material | |
| CN110534712A (en) | A kind of black phosphorus-titanium dioxide-carbon compound cathode materials and preparation method and application | |
| CN102983317A (en) | Silicon-based composite material and preparation method thereof, silicon-carbon composite material and lithium ion battery | |
| CN111029558A (en) | Silicon-carbon composite negative electrode material with hollow core-shell structure and preparation method thereof | |
| CN116799210A (en) | Composite lithium supplementing material and preparation method thereof, lithium supplementing coating and preparation method thereof, and lithium battery | |
| CN114792791B (en) | Negative electrode material, preparation method and application thereof | |
| CN113130858A (en) | Silicon-based negative electrode material, preparation method thereof, battery and terminal | |
| CN114497508A (en) | Power type artificial graphite composite material and preparation method thereof | |
| CN111900352A (en) | Lithium titanate silicon-based composite negative electrode material and preparation method thereof | |
| CN111193013A (en) | Preparation method of silicon-carbon negative electrode material for lithium ion battery | |
| CN108288705B (en) | Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof | |
| CN113241441A (en) | Pomegranate-like structure silicon-based composite material, and preparation method and application thereof | |
| CN114105133B (en) | Graphite-silicon/silicon oxide-carbon composite material and preparation method and application thereof | |
| CN114709383A (en) | Modified lithium ion battery anode material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190611 |
|
| RJ01 | Rejection of invention patent application after publication |