CN109216686A - A kind of lithium ion battery silicon-carbon composite material and preparation method - Google Patents
A kind of lithium ion battery silicon-carbon composite material and preparation method Download PDFInfo
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Abstract
The invention discloses a kind of lithium ion battery silicon-carbon composite material and preparation methods, belong to technical field of lithium ion.The composite material includes: the composite particles comprising nano-silicon, carbon material, nanometer inert metal or metal silicide, and it is coated on the carbon-coating on the composite particles surface, the composite material is the porous secondary structure with micron-scale, it is mixed by nano-silicon, carbon material, metal salt and organic carbon source solution, is made through spray pyrolysis and sintering carbonization.The composite material can give full play of the synergistic effect of silicon, carbon and metal material, and the electrochemistry capacitance of silicon materials is high, and carbon material increases electric conductivity, and inert metal or metal silicide can further increase electric conductivity and reduce volume change；Porous secondary structure effectively improves tap density and has adapted to the volume expansion of silicon to mitigate mechanical stress.
Description
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of lithium ion battery silicon-carbon composite material and its system
Preparation Method.
Background technique
Since with good charge and discharge cycles stability, graphite-like carbon negative pole material is still widely used in business lithium
In ion battery, but its theoretical capacity is very limited (372mAh/g).With the development of consumer electronics and electric car, people
Higher and higher to the energy density requirement of lithium ion battery, there is an urgent need to develop the negative electrode of lithium ion battery material of new high capacity for this
Material.In all kinds of novel storage lithium titanate cathode materials, silicon possesses highest theoretical capacity (4212mAh/g)；Silicon based anode material simultaneously
Also have many advantages, such as that from a wealth of sources, cheap, intercalation potential is low, there is no toxicity.Therefore silicon, which is considered next-generation, most business
Change the negative electrode material of application prospect.
However, there are serious volume expansion and contractions in charge and discharge process for silicon, this can make the continuous dusting of silicon, and then lead
It causes gradually to disengage and lose the electrical contact with collector between electrode active material and collector, so that electrode cycle performance is rapid
Decline.The destruction of simultaneous electrode structure, the silicon face newly exposed can be formed constantly during with electrolyte contacts
New solid electrolyte film (SEI), to be difficult to form stable SEI, this will lead to efficiency for charge-discharge reduction, and capacity attenuation adds
It is acute.In addition, silicon itself is semiconductor material, conductivity is low, and conductive agent need to be added to improve the electronic conductance of electrode.For effectively
Silicon materials are applied in lithium ion battery, need to improve its first charge-discharge coulombic efficiency and electrochemical cycle stability.
Currently, acquisition capacity is higher, and cyclicity is more stable in order to reduce volume expansion of silicon during lithium ion deintercalation
Silicon based anode material, research work both domestic and external is concentrated mainly on the nanosizing of silicon materials and prepared based on nano-silicon each
The silicon based composite material of kind pattern, structure.
Porous silicon/carbon composite and application are prepared by raw material of diatomite as CN102208636A discloses one kind, is had
Body discloses: preparing porous silicon by silicon source of diatomite first, then compound to be prepared for porous silicon/charcoal multiple porous silicon and carbon material
Condensation material is to reduce preparation cost and alleviate the bulk effect of silicon.
Nian Liu et al. reports a kind of Si@C of yolk-eggshell structure.Si is completely coated on it by very thin carbon-coating
In, intermediate void layer allows Si Particle free to expand without destroying carbon-coating.At 0.1C, Si@C discharge capacity is reachable
2800mAh/g；After 1000 circulations, capacity keeps 74% (Nian Liu et al.A yolk-shell designfor
stabilized and scalable Li-ion battery alloy anodes[J].Nano Lett,2012,12(6):
3315)。
Sujong Chae etc. is prepared for Fe-Cu-Si trielement composite material using spray pyrolysis, and reversible capacity reaches
1287mAh/g, coulombic efficiency is up to 91% (Sujong Chae al.Micron-sized Fe-Cu-Si ternary
composite anodes for high energy Li-ion batteries[J].Energy Environ.Sci.,
2016,9,1251-1257)。
CN102790204A discloses a kind of preparation method of silicon carbon lithium ion battery cathode, specific open: first
Polymer Solution and silicon powder, graphite are mixed to get mixed liquor；Then freeze-drying removes solvent, and final high temperature sintering obtains
Silicon carbon lithium ion battery cathode.
CN104332594A discloses a kind of silicon based anode material and its preparation method and application, the silicon based anode material packet
Graphene, silicon nanoparticle and nano-metal particle with layer structure are included, silicon nanoparticle and nano-metal particle are embedding
In the layer structure of the graphene.
Although these silicon based anode materials alleviate the volume occurred when the embedding de- lithium of silicon materials itself to a certain extent
Expansion and blockage effect, but since it is with biggish specific surface area, it can disappear in the contact in cyclic process and with electrolyte
A large amount of lithium ion is consumed, so as to cause the increase of side reaction and the reduction of coulombic efficiency, thereby reduces cycle performance and capacity
Conservation rate；On the other hand, the composite materials such as these single silico-carbo, silicon-metals, which can't be fully solved existing for silicon materials, asks
Topic or Volumetric expansion can not be solved thoroughly or conductivity is also wait improve or preparation cost is high, to influence it
Practical application.
Summary of the invention
The purpose of the present invention is to provide it is a kind of it is low in cost, specific capacity is high, Volumetric expansion is low, conductivity is high, with
The good Si-C composite material of battery electrolyte compatibility.
To achieve the above object, the present invention provides a kind of lithium ion battery silicon-carbon composite material, which includes:
Composite particles comprising nano-silicon, carbon material, nanometer inert metal or metal silicide, and it is coated on the composite particles table
The carbon-coating in face；The lithium ion battery silicon-carbon composite material is the porous secondary structure of micron-scale.
Composite material provided by the invention is the porous secondary structure with micron-scale, wherein being embedded in many nano-scales
Silicon, carbon, inert metal or metal silicide grain, while outer layer uniformly coats pyrolytic carbon can give full play of silicon, carbon and
The synergistic effect of metal material；And porous secondary structure effectively increases tap density and adapts to the volume expansion of silicon to mitigate
Mechanical stress.
Preferably, the partial size of the nano-silicon is 50-900nm, the partial size of carbon material is 10nm-100 μm, nanometer inertia
The partial size of metal or metal silicide is 10-100nm, carbon layers having thicknesses 10-50nm.
Preferably, by percentage to the quality, in the lithium ion battery silicon-carbon composite material nano-silicon be 10-60%,
Carbon material is 30-80%, nanometer inert metal or metal silicide are 5-20%, carbon-coating 5-20%.By adjusting silicon, carbon materials
Material and inactive metal sill, can control volume expansion, coulombic efficiency and the specific capacity of composite material, to regulate and control electrode
The capacity and cycle life of material.
Preferably, the pore size of the lithium ion battery silicon-carbon composite material is 30-l00nm, porosity 10-
100%.Hole is conducive to electrolyte and infiltrates and accelerate ionic conduction.
The present invention also provides a kind of method for preparing the lithium ion battery silicon-carbon composite material, the method includes
Following steps:
(1) nano-silicon, carbon material, metal salt and organic carbon source solution are mixed, obtains precursor solution；
(2) precursor solution is spray-dried, obtains Si-C-M composite material first product；
(3) it disperses Si-C-M composite material first product in organic carbon source solution, after removing solvent again in an inert atmosphere
Sintering carbonization, is made the lithium ion battery silicon-carbon composite material.
Preferably, after the nano-silicon is by silica material and metallic reducing agent mixing and ball milling, then be soaked in acid
Impurity is removed, separation is made.Silica material causes reduction reaction in Mechanical Milling Process, obtains silicon nanoparticle.More
To be preferred, the partial size of nano-silicon obtained is 50-200nm.
The present invention prepares nano-silicon using the method for mechanical ball mill from the silica material of low cost, greatly saves
Production cost is saved, preferably, silica material and metallic reducing agent 1:2 ball milling on ball mill in molar ratio.
Preferably, the silica material be diatomite, mesoporous silicon oxide, porous molecular screen, quartz or
Artificial synthesized silica；The metallic reducing agent is magnesium, calcium, lithium, sodium or potassium metal powder.The acid be hydrochloric acid or
Sulfuric acid.
Preferably, the carbon material is natural graphite, artificial graphite, expanded graphite, graphene, carbon black, active carbon
At least one of with carbon nanotube.The partial size of the carbon material is 10nm-100 μm.
Preferably, the metal salt is at least one of iron, copper, zinc, manganese, cobalt, nickel salt.More preferably, described
Metal salt is ferric nitrate, copper nitrate or manganese nitrate.
More preferably, nano-silicon: carbon material: the mass ratio of metal salt is 1:1:0.5 in step (1).
Preferably, in step (1) and (3), the organic carbon source be sucrose, glucose, fructose, citric acid, starch,
Cellulose, pitch, coal tar, butadiene-styrene rubber, polyvinyl alcohol, carboxymethyl cellulose, polyvinyl chloride, polystyrene, polyacrylonitrile,
At least one of furfural resin, phenolic resin, epoxy resin.
The solvent that the organic carbon source uses can for water, ethyl alcohol, butanol, methanol, acetone, ethyl acetate, tetrahydrofuran,
N-Methyl pyrrolidone, pyrrole instigate, chloroform or hexamethylene.
More preferably, the organic carbon source solution is glucose solution, aqueous citric acid solution or sugarcane in step (1)
Sugar aqueous solution；In step (3), the organic carbon source solution be pitch-tetrahydrofuran solution, polyacrylonitrile-ethanol solution or
Epoxy resin-ethanol solution.
In step (2), precursor solution is atomized using spray drying process, as solvent volatilization and presoma are decomposed
Form microcellular structure.The present invention is by atomization so that nano-silicon, carbon material, metallic are evenly distributed on the porous of carbon source cladding
In microballoon.Preferably, being brought by carrier gas spraying hot in situ in 200-900 DEG C of progress in reacting furnace after precursor solution atomization
Solution.
In step (3), further carbon source carbonization package facilitates the structural stability and electric conductivity that increase composite material.
The carbon-coating is agraphitic carbon.The temperature of the sintering carbonization is 600-1200 DEG C.In the step, it can be adjusted by carbon source cladding
Control the hole and structure of composite material.Preferably, the mass ratio of Si-C-M composite material first product and organic carbon source is 4:1.
In heating carbonisation, metal salt generates inert metal or metal silicide grain, further increases conductive
Property and reduce volume change, to reduce side effect, improve coulombic efficiency.
It is that the present invention has the utility model has the advantages that
(1) the porous second level knot with micron-scale that Si-C composite material provided by the invention is made of nanocrystal
Structure, the material can give full play of the synergistic effect of silicon, carbon and metal material, and the electrochemistry capacitance of silicon materials is high, carbon material
Increase electric conductivity, inert metal or metal silicide can further increase electric conductivity and reduce volume change；Porous second level knot
Structure effectively improves tap density and has adapted to the volume expansion of silicon to mitigate mechanical stress.
(2) from inexpensive silica material nano-silicon is first made using the method for mechanical ball mill, then in the present invention
Again by mixing with carbon material, metal salt and organic carbon source, spray pyrolysis, and the method for pyrolysis carbonization are prepared by nanocrystal
The micron Si-C composite material of composition, this method have many advantages, such as low in cost, and operating procedure is simple.
Detailed description of the invention
Fig. 1 is the battery first charge-discharge curve graph based on Si-C composite material made from embodiment 1；
Fig. 2 is the circulating battery curve graph based on Si-C composite material made from embodiment 1.
Specific embodiment
Below by specific embodiment, the present invention is further elaborated, it is noted that following instance is merely to illustrate
The present invention rather than limit the scope of the invention.In addition, it should also be understood that, those skilled in the art according to above-mentioned invention do by content
Nonessential improved adjustment out, should belong to protection scope of the present invention.
Embodiment 1
Firstly, being in molar ratio 1:2 ball milling on ball mill by silica material diatomite and magnesium powder, then by ball milling
Mixture afterwards is immersed in hydrochloric acid, then uses deionized water, the washing such as ethyl alcohol, and separation obtains nano-silicon after drying.
Then the nano silica fume particle for being 50nm by the partial size of 0.2g synthesis, the graphite of 0.2g, the ferric nitrate difference of 0.1g
It is added to alone in the aqueous solution for the glucose that concentration is 0.2M, ultrasonic disperse 30min forms the suspension or solution hooked；
Then three kinds of solution are put together and is continuesd to mix uniformly.
Secondly, above-mentioned resulting mixed liquor to be carried out using spray drying process at 200 DEG C to spraying cracking, it is multiple that Si-C-M is made
Condensation material first product；
Then, the above-mentioned Si-C composite material of 0.2g and 0.05g pitch are used to ultrasonic disperse 90min, shape in tetrahydrofuran
It at uniform suspension, is then dried in vacuo at 80 DEG C, obtains the mixture of Si-C-M composite particles and pitch.
Finally the mixture of Si-C-M composite particles and pitch after drying is put into tube furnace, under protection of argon gas,
Roasting charing is carried out at 900 DEG C to get final Si-C-M composite material.
Embodiment 2
Firstly, being in molar ratio 1:2 ball milling on ball mill by silica material porous molecular screen and lithium block, then will
Mixture after ball milling is immersed in sulfuric acid, then uses deionized water, the washing such as ethyl alcohol, and separation obtains nano-silicon after drying.
Then the nano silica fume particle for being 100nm by the partial size of 0.2g synthesis, the graphite of 0.2g, the copper nitrate difference of 0.1g
It is added to alone in the aqueous solution for the citric acid that concentration is 0.2M, ultrasonic disperse 30min forms the suspension or solution hooked；
Then three kinds of solution are put together and is continuesd to mix uniformly.
Secondly, above-mentioned resulting mixed liquor to be carried out using spray drying process at 500 DEG C to spraying cracking, it is multiple that Si-C-M is made
Condensation material first product；
Then, the above-mentioned Si-C-M composite material first product of 0.2g and 0.05g polyacrylonitrile are used into ultrasonic disperse in ethanol
90min forms uniform suspension, is then dried in vacuo at 80 DEG C, and Si-C-M composite particles and polyacrylonitrile are obtained
Mixture.
Finally the mixture of Si-C-M composite particles and polyacrylonitrile after drying is put into tube furnace, is protected in argon gas
Under, roasting charing is carried out at 1000 DEG C to get final Si-C-M composite material.
Embodiment 3
Firstly, being in molar ratio 1:2 ball milling on ball mill by silica material quartz and sodium block, then by ball milling
Mixture afterwards is immersed in hydrochloric acid, then uses deionized water, the washing such as ethyl alcohol, and separation obtains nano-silicon after drying.
Then the nano silica fume particle for being 200nm by the partial size of 0.2g synthesis, the graphite of 0.2g, the manganese nitrate difference of 0.1g
It is added to alone in the aqueous solution for the sucrose that concentration is 0.2M, ultrasonic disperse 30min forms the suspension or solution hooked；So
Three kinds of solution are put together afterwards and are continuesd to mix uniformly.
Secondly, above-mentioned resulting mixed liquor to be carried out using spray drying process at 700 DEG C to spraying cracking, it is multiple that Si-C-M is made
Condensation material first product；
Then, the above-mentioned Si-C composite material first product of 0.2g and 0.05g epoxy resin are used into ultrasonic disperse in ethanol
90min forms uniform suspension, is then dried in vacuo at 80 DEG C, and Si-C-M composite particles and epoxy resin are obtained
Mixture.
Finally the mixture of Si-C-M composite particles and epoxy resin after drying is put into tube furnace, is protected in argon gas
Under, roasting charing is carried out at 1200 DEG C to get final Si-C-M composite material.
Embodiment 4
Firstly, being in molar ratio 1:2 ball milling on ball mill by silica material diatomite and magnesium powder, then by ball milling
Mixture afterwards is immersed in hydrochloric acid, then uses deionized water, the washing such as ethyl alcohol, and separation obtains nano-silicon after drying.
Then the nano silica fume particle for being 50nm by the partial size of 0.2g synthesis, the graphite of 0.2g and the carbon nanotube of 0.05g,
The ferric nitrate of 0.1g is added to alone respectively in the aqueous solution for the glucose that concentration is 0.2M, and ultrasonic disperse 30min, formation hooks
Suspension or solution；Then four kinds of solution are put together and is continuesd to mix uniformly.
Secondly, above-mentioned resulting mixed liquor to be carried out using spray drying process at 200 DEG C to spraying cracking, it is multiple that Si-C-M is made
Condensation material first product；
Then, the above-mentioned Si-C composite material first product of 0.2g and 0.05g pitch are used into ultrasonic disperse in tetrahydrofuran
90min forms uniform suspension, is then dried in vacuo at 80 DEG C, and the mixing of Si-C-M composite particles and pitch is obtained
Object.
Finally the mixture of Si-C-M composite particles and pitch after drying is put into tube furnace, under protection of argon gas,
Roasting charing is carried out at 900 DEG C to get final Si-C-M composite material.
Application examples
Si-C composite material prepared by embodiment 1-4 is used as conductive agent, carboxylic first as negative electrode active material, carbon black (SP)
Base sodium cellulosate (CMC) and butadiene-styrene rubber (SBR) are used as bonding agent, according to quality than Si-C composite material: SP:CMC:SBR=
90:5:2:3 mixing, using deionized water as dispersing agent, is made solid content about 50%, viscosity 2000- after agitated
The slurry of 4000mPa.s is coated on copper foil, button cell or flexible packaged battery is prepared into after drying, cold pressing, cut-parts, slitting
The cathode pole piece in pond；The LiPF that electrolyte is l M with concentration6Lithium salts, with the ethylene carbonate of mass ratio EC:EMC:DEC=1:1:1
The mixture of ester, methyl ethyl carbonate and diethyl carbonate is as non-aqueous organic solvent.
The button cell prepared as negative electrode active material through the above method to Si-C composite material prepared by embodiment 1 exists
Current density is 200mA/g, and voltage range carries out initial capacity test and cycle performance test under the conditions of being 0.01-2.5V, point
Result shown in Fig. 1 and Fig. 2 is not obtained.
As seen from Figure 1, Figure 2, which has excellent discharge capacity.Under the current density of 200mA/g, Si-C-M electricity
Pole first circle specific discharge capacity is 1113mAh/g, and first circle coulombic efficiency is 87%.Its capacity remains at after 80 circle circulations
970mAh/g or so, and its coulombic efficiency in 80 circle circulations maintains 100% or so.This shows that porous second level micron is multiple
Condensation material shows preferable structural advantage, can provide enough spaces effectively to accommodate the expansion and dusting of Si.The silicon
Carbon composite excellent electrochemical performance can be used as the good negative electrode material of lithium ion battery.
Claims (10)
1. a kind of lithium ion battery silicon-carbon composite material characterized by comprising include nano-silicon, carbon material, nanometer inertia gold
The composite particles of category or metal silicide, and it is coated on the carbon-coating on the composite particles surface；The lithium ion battery silicon-carbon
Composite material is the porous secondary structure of micron-scale.
2. lithium ion battery silicon-carbon composite material as described in claim 1, which is characterized in that the partial size of the nano-silicon is
50-900nm, the partial size of carbon material are 10nm-100 μm, and the partial size of nanometer inert metal or metal silicide is 10-100nm, carbon
Layer is with a thickness of 10-50nm.
3. lithium ion battery silicon-carbon composite material as described in claim 1, which is characterized in that by percentage to the quality, described
In lithium ion battery silicon-carbon composite material nano-silicon be 10-60%, carbon material 30-80%, nanometer inert metal or metallic silicon
Compound is 5-20%, carbon-coating 5-20%.
4. lithium ion battery silicon-carbon composite material as described in claim 1, which is characterized in that the lithium ion battery silicon-carbon
The pore size of composite material is 30-100nm, porosity 10-100%.
5. the preparation method of lithium ion battery silicon-carbon composite material according to any one of claims 1-4, which is characterized in that packet
Include following steps:
(1) nano-silicon, carbon material, metal salt and organic carbon source solution are mixed, obtains precursor solution；
(2) precursor solution is spray-dried, obtains Si-C-M composite material first product；
(3) it disperses Si-C-M composite material first product in organic carbon source solution, is sintered in an inert atmosphere again after removing solvent
The lithium ion battery silicon-carbon composite material is made in carbonization.
6. preparation method as claimed in claim 5, which is characterized in that the nano-silicon is restored by silica material and metal
It after agent mixing and ball milling, then is soaked in acid and removes impurity, separation is made.
7. preparation method as claimed in claim 6, which is characterized in that the silica material is diatomite, mesoporous two
Silica, porous molecular screen, quartz or artificial synthesized silica；The metallic reducing agent be magnesium, calcium, lithium, sodium or
Potassium metal powder.
8. preparation method as claimed in claim 5, which is characterized in that the carbon material is natural graphite, artificial graphite, swollen
At least one of swollen graphite, graphene, carbon black, active carbon and carbon nanotube.
9. preparation method as claimed in claim 5, which is characterized in that the metal salt is iron, copper, zinc, manganese, cobalt, nickel salt
At least one of.
10. preparation method as claimed in claim 5, which is characterized in that in step (2), after precursor solution atomization, by carrier gas
It brings into reacting furnace in 200-900 DEG C of progress spray pyrolysis in situ.
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| CN109755555A (en) * | 2019-01-22 | 2019-05-14 | 山东玉皇新能源科技有限公司 | Silicon carbon material and preparation method thereof |
| CN110993910A (en) * | 2019-11-29 | 2020-04-10 | 国联汽车动力电池研究院有限责任公司 | Silicon-carbon composite material and preparation method thereof |
| CN111755669A (en) * | 2019-03-27 | 2020-10-09 | 贝特瑞新材料集团股份有限公司 | Composite material, preparation method and application thereof |
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| CN114759174A (en) * | 2021-11-12 | 2022-07-15 | 中国神华煤制油化工有限公司 | Spherical silicon-carbon negative electrode material, preparation method and device thereof, lithium battery negative electrode and lithium battery |
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| CN114497482B (en) * | 2021-12-31 | 2024-03-22 | 长沙矿冶研究院有限责任公司 | Silicon-carbon composite material and preparation method thereof |
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| CN117199327A (en) * | 2023-11-07 | 2023-12-08 | 南通大学 | Quick-charging silicon-based negative electrode material for lithium battery and preparation method thereof |
| CN117199327B (en) * | 2023-11-07 | 2024-05-03 | 南通大学 | Quick-charging silicon-based negative electrode material for lithium battery and preparation method thereof |
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