CN101439972B - Silicon-carbon composite material, preparation thereof, battery cathode and lithium ionic cell - Google Patents
Silicon-carbon composite material, preparation thereof, battery cathode and lithium ionic cell Download PDFInfo
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Abstract
The invention relates to a silicon-carbon composite material, which contains nano-silicon/carbon nanotube composite particles and amorphous carbon, wherein the amorphous carbon is coated on the surfaces of the composite particles. A method for preparing the material comprises the following steps: dispersing the nano-silicon and the carbon nanotubes in a dispersant, and removing the dispersant to obtain the nano-silicon/carbon nanotube composite particles; and contacting the nano-silicon/carbon nanotube composite particles with an amorphous carbon precursor solution, and removing a solvent to carbonize the amorphous carbon precursor. The invention also provides a negative pole of a lithium ion cell made from the composite material. The method for preparing the composite material is simple, the process is easy to control, and a cell made of the negative pole made from the composite material has a lower first irreversible specific capacity, higher specific capacity and excellent cycling performance.
Description
Technical field
The present invention relates to a kind of Si-C composite material and preparation method thereof, and the battery cathode and the lithium ion battery that use this material to make.
Background technology
Development along with electronics and information industry, the miniaturization of electronic equipment and high performance high speed development improve constantly the battery capacity density requirements, add since the capacity of carbon back negative material almost near the theoretical value of 372mAh/g, people sight invested silicon, tin, aluminium and antimony etc. can with the lithium electrochemical alloyed metal (AM).Wherein, silicon is the most attractive a kind of, and its theoretical capacity is up to 4200mAh/g.But they embed and deviate from the process volume at lithium ion and expand and shrink, the variation that electrically contacts that causes active material and collector, and then causing capacity and the cycle performance variation of material, the battery life of making is very short, has hindered the practical of these materials.In order to address the above problem, people have researched and developed the negative pole that the composite material of silicon and carbon is made, such as disclosed nano-sized carbon silicon composite among the CN 1903793A, but although this material is very large owing to specific area, discharge capacity is higher, but the lithium consumption of the solid electrolyte interface film (SEI film) that the surface forms is serious, the first charge-discharge irreversible capacity is higher, and accelerates in the decay of the rear electrode capacity that repeatedly circulates, from a practical in addition segment distance.In the prior art, be difficult to make the recursive nature of silicon/carbon composite to obtain preferably effect.
Summary of the invention
The object of the invention is to provides a kind of lithium ion battery anode active material with higher capacity and excellent cycling performance and preparation method thereof in order to overcome the poor shortcoming of lithium ion battery negative cycle performance that Si-C composite material is made in the prior art.
Another object of the present invention is to provide a kind of lithium ion battery negative that uses negative material of the present invention to make.
The 3rd purpose of the present invention is to provide a kind of lithium ion battery that uses negative pole of the present invention to make.
The invention provides a kind of Si-C composite material, this composite material contains nano-silicon/carbon nano-tube composite particles and amorphous carbon, and described amorphous carbon is coated on described composite particles surface.
The invention provides a kind of preparation method of Si-C composite material, the method comprises nano-silicon and carbon nanotube dispersed in dispersant, removes dispersant, obtains nano-silicon/carbon nano-tube composite particles; Nano-silicon/carbon nano-tube composite particles is contacted with the amorphous carbon precursor solution, desolventizing, and make the charing of amorphous carbon presoma.
The present invention also provides a kind of silicon-carbon composite lithium ion battery cathode, and this negative pole comprises negative current collector and the negative material that is coated on the collector, wherein, and the active material of described negative material composite material provided by the invention.
The present invention also provides a kind of lithium ion battery, and this battery comprises battery container, electrode group and electrolyte, and electrode group and electrolyte are sealed in the battery container, and the electrode group comprises positive pole, barrier film and negative pole, and wherein, described negative pole is negative pole of the present invention.
Carbon nano-tube has good electricity, mechanical property, the structure high resilience.Carbon nano-tube and nano-silicon are compound can to form many nano level spaces, and these spaces can become the space of the expansion of silicon, thereby slow down the expansion of silicon to the impact of coating layer; Carbon nano-tube itself also has large lithium storage content; Simultaneously, surperficial amorphous carbon layer can be alleviated the in use impact of the height storage lithium situation of electrolyte and electrode surface SEI film of nano-silicon/carbon nano tube compound material, reduces the irreversible capacity that battery circulates first.Its preparation method is simple, and process is easily controlled, and the battery made from the negative pole of this material preparation has lower first irreversible capacity, higher specific capacity and excellent cycle performance.
Embodiment
Si-C composite material provided by the invention contains nano-silicon/carbon nano-tube composite particles and amorphous carbon, and described amorphous carbon is coated on described composite particles surface.
The particle diameter of described nano-silicon is the 20-100 nanometer; The diameter of described carbon nano-tube is the 20-100 nanometer, and length is the 0.5-2 micron.Take the nano-silicon of 100 weight portions as benchmark, the content of carbon nano-tube can be the 1-50 weight portion, is preferably the 1-25 weight portion; The content of amorphous carbon can be the 30-200 weight portion, is preferably the 40-150 weight portion.
The preparation method of Si-C composite material provided by the invention comprises nano-silicon and carbon nanotube dispersed in dispersant, removes dispersant, obtains nano-silicon/carbon nano-tube composite particles; Nano-silicon/carbon nano-tube composite particles is contacted with the amorphous carbon precursor solution, desolventizing, and make the charing of amorphous carbon presoma.
The particle diameter of described nano-silicon is the 20-100 nanometer; The diameter of described carbon nano-tube is the 20-100 nanometer, and length is the 0.5-2 micron.
The dispersant that is used for dispersing nanometer silicon and carbon nano-tube can be the various liquid that can make nano-silicon and carbon nanotube dispersed, for example, can be water, ethanol, propyl alcohol, propylene glycol or their mixture.The consumption of described dispersant is that per 100 gram nano-silicons adding 1-15 rise dispersant.
The consumption of described nano-silicon, carbon nano-tube and amorphous carbon presoma makes in the composite material that obtains, and take the nano-silicon of 100 weight portions as benchmark, the content of carbon nano-tube is the 1-50 weight portion, is preferably the 1-25 weight portion; The content of amorphous carbon is the 30-200 weight portion, is preferably the 40-150 weight portion.
Described amorphous carbon precursor solution is dissolved in the solvent by the amorphous carbon presoma and forms.Described amorphous carbon presoma can for forming the organic substance of amorphous carbon after any thermal cracking, be preferably one or more in resin, pitch, glucose, sucrose, starch, asccharin, benzene, naphthalene and the benzene naphthalene copolymer; Solvent for use can be any common solvent that can make selected presoma dissolving, for example can be in acetone, absolute ethyl alcohol, 1-METHYLPYRROLIDONE, chloroform, the cyclohexane one or more.Take the 100 amorphous carbon presomas that restrain as benchmark, the addition of solvent is the 150-3000 milliliter.
Described desolventizing and carbonization process are vaporization at high temperature solvent and the charing under the inert gas shielding.The method of described solvent flashing is warmed up to 200-400 ℃ for being coated with the nano-silicon of amorphous carbon presoma/carbon nano-tube composite particles under inert gas shielding with 0.5-10 ℃/minute speed, is incubated 2-10 hour; The method of described charing be with the product after the desolventizing under inert gas shielding, be heated to 850-1200 ℃ with 1-10 ℃/minute speed, be incubated 2-8 hour.At last, naturally cool to normal temperature.Used inert gas can be in nitrogen and the group 0 element gas one or more.
Desolventize finish with charing after, it can also be ground, sieves.
Under the preferable case, the preparation method of Si-C composite material provided by the invention comprises the steps:
(1) preparation of nano-silicon/carbon nano-tube composite particles
Take deionized water and ethanol volume ratio as 2-9: 1 configuration solution.Take total solution weight as benchmark, add the surfactant of 0.2-0.6 % by weight, stir a period of time, be mixed with solution.Then put into nano-silicon and carbon nano-tube, continue to stir 20-60 minute.Filtration, 60-80 ℃ oven dry obtain nano-silicon/carbon nano-tube composite particles.
(2) composite particles is contacted with the amorphous carbon precursor solution
Preparation amorphous carbon precursor solution is preferably resin/ethanolic solution and/or pitch/tetrahydrofuran solution, and take the 100 amorphous carbon presomas that restrain as benchmark, the addition of solvent is the 300-1000 milliliter.The nano-silicon that makes in the adding step (1) under stirring/carbon nano-tube composite particles continues to stir 20-60 minute.Filter, obtain the nano-silicon of coated with carbon presoma/carbon nano-tube combination product.
(3) desolventize and charing
The combination product that step (2) obtains is put in the high temperature furnace that is connected with inert gas, be heated to 200-400 ℃ with 0.5-10 ℃ of/minute intensification, be incubated 2-10 hour; Be heated to 800-1200 ℃ of insulation 2-8 hour with 1-10 ℃/minute again.Naturally cool to normal temperature.Take out material, the soft grinding sieved, and namely obtains product.
Silicon-carbon composite lithium ion battery cathode provided by the invention comprises negative current collector and the negative material that is coated on the collector, and wherein, the active material of described negative material is composite material provided by the invention.
Described negative current collector can be for negative pole conducting base conventional in the lithium ion battery, such as stamped metal, and metal forming, net metal, foamed metal uses Copper Foil as negative current collector in specific embodiments of the present invention.
Described negative material comprises negative electrode active material and adhesive.Described negative electrode active material is composite material provided by the invention; The kind of described adhesive and content are conventionally known to one of skill in the art, for example one or more in fluorine resin and polyolefin compound such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), butadiene-styrene rubber (SBR), hydroxypropyl methylcellulose, sodium carboxymethylcellulose, hydroxyethylcellulose, the polyvinyl alcohol; In general, according to the difference of adhesive therefor kind, take the weight of negative electrode active material as benchmark, the content of adhesive is the 0.01-10 % by weight, is preferably the 0.02-5 % by weight.
Lithium ion battery provided by the present invention comprises electrode group and electrolyte, and described electrode group and electrolyte are sealed in the battery container, and described electrode group comprises positive pole, barrier film and negative pole.Except described negative pole adopts negative pole provided by the invention, can use conventional positive pole, barrier film and electrolyte.
Described positive pole comprises plus plate current-collecting body and the positive electrode active materials that is coated on the plus plate current-collecting body.
Described positive electrode active materials is not particularly limited, and can be the positive electrode active materials of the embedded removal lithium embedded of this area routine, a kind of or its mixture: the Li in the preferred following material
xNi
1-yCoO
2(wherein, 0.9≤x≤1.1,0≤y≤1.0), Li
1+aM
bMn
2-bO
4(wherein ,-0.1≤a≤0.2,0≤b≤1.0, M is a kind of in lithium, boron, magnesium, aluminium, titanium, chromium, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine, the element sulphur), Li
mMn
2-nB
nO
2(wherein, B is transition metal, 0.9≤m≤1.1,0≤n≤1.0).
Described plus plate current-collecting body is conventionally known to one of skill in the art, for example can be selected from aluminium foil, Copper Foil or various Punching steel strip.
According to lithium ion battery provided by the invention, membrane layer is arranged between positive pole and the negative pole, has electrical insulation capability and liquid retainability energy.Described membrane layer can be selected from and well known to a person skilled in the art various membrane layers used in the lithium ion battery, for example polyolefin micro porous polyolefin membrane, polyethylene felt, glass mat or ultra-fine fibre glass paper.
Described electrolyte can be the electrolyte of various routines, for example nonaqueous electrolytic solution.Described nonaqueous electrolytic solution is the solution that electrolyte lithium salt forms in nonaqueous solvents.Can be selected from lithium hexafluoro phosphate (LiPF such as electrolyte lithium salt
6), lithium perchlorate (LiClO
4), LiBF4 (LiBF
4), hexafluoroarsenate lithium (LiAsF
6), hexafluorosilicic acid lithium (LiSiF
6), tetraphenyl lithium borate (LiB (C
6H
5)
4), lithium chloride (LiCl), lithium bromide (LiBr), chlorine lithium aluminate (LiAlCl
4) and fluorocarbon based Sulfonic Lithium (LiC (SO
2CF
3)
3), LiCH
3SO
3, LiN (SO
2CF
3)
2In one or more.Nonaqueous solvents can be selected from chain acid esters and ring-type acid esters mixed solution, wherein the chain acid esters can be fluorine-containing for dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), methyl propyl carbonate (MPC), dipropyl carbonate (DPC) and other, sulfur-bearing or contain in the chain organosilane ester of unsaturated bond one or more.The ring-type acid esters can (γ-BL), sultone and other be fluorine-containing, sulfur-bearing or contain in the ring-type organosilane ester of unsaturated bond one or more for ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton.
According to lithium ion battery provided by the invention, the preparation method of this battery is well known for the person skilled in the art, and in general, the preparation method of this battery comprises the electrode group is inserted in the battery case, adds electrolyte, and then sealing obtains lithium ion battery.Wherein, the method for sealing, the consumption of electrolyte is conventionally known to one of skill in the art.
The invention will be further described for the following examples.
Embodiment 1
The present embodiment is used for illustrating the preparation of composite material of lithium ion battery cathode provided by the invention.
(1) preparation of nano-silicon/carbon nano-tube composite particles
In 1500 ml beakers, successively add 600 ml deionized water and 150 milliliters of ethanol and 20 gram polyvinyl alcohol, stir after 30 minutes, slowly add the mixture that contains 10 gram nano-silicons and 0.6 gram carbon nano-tube under the stirring condition, the nano-silicon particle diameter is the 20-50 nanometer, carbon nano-tube diameter 20-50 nanometer, length 1-2 micron stirs after 40 minutes, filter 80 ℃ of oven dry.
(2) composite particles is contacted with the amorphous carbon precursor solution
The nano-silicon that step (1) is obtained/carbon nano-tube composite particles joins in the solution that contains 15 gram epoxy resin and 400 milliliters of ethanol that stirs in advance, stirs after 40 minutes filtration.
(3) desolventize and charing
Step (2) filtered the solid product obtain under the N2 protection, in high temperature furnace, be warming up to 400 ℃ with 5 ℃/minute, be incubated 1 hour, be warming up to 900 ℃ with 5 ℃/minute again, be incubated 3 hours, then naturally be cooled to below 100 ℃, from high temperature furnace, take out.Pulverize, excessively behind 200 mesh sieves, namely obtain 17.5 gram products, be denoted as E1.
Embodiment 2
The present embodiment is used for illustrating the preparation of composite material of lithium ion battery cathode provided by the invention.
(1) preparation of nano-silicon/carbon nano-tube composite particles
With the method identical with embodiment step (1), different is that the ethanol of adding is 80 milliliters; Replace 20 gram polyvinyl alcohol with 20 gram polyvinylpyrrolidones; And the consumption of carbon nano-tube changes 2 grams into.
(2) composite particles is contacted with the amorphous carbon precursor solution
With the method identical with embodiment step (2), different is to contain the solution that 24 1000 milliliters of tetrahydrofuran solutions that restrain pitch prills replace containing 15 gram epoxy resin and 400 milliliters of ethanol.
(3) desolventize and charing
With the method identical with embodiment step (3), product 34 grams are denoted as E2.
Embodiment 3
The present embodiment is used for illustrating the preparation of composite material of lithium ion battery cathode provided by the invention.
(1) preparation of nano-silicon/carbon nano-tube composite particles
With the method identical with embodiment step (1), the consumption of carbon nano-tube that different is changes 1 gram into.
(2) composite particles is contacted with the amorphous carbon precursor solution
With the method identical with embodiment step (2), different is that the epoxy resin of adding is 20 grams.
(3) desolventize and charing
With the method identical with embodiment step (3), product 23.2 grams are denoted as E3.
Comparative Examples 1
This Comparative Examples is used for the preparation of explanation prior art used as negative electrode of Li-ion battery Si-C composite material.
Take by weighing 0.001 gram iron powder and 10 gram silicon grains (average grain diameter is 5 microns), mixed grinding was placed in the graphite boat after 5 hours, in the tube furnace of packing into, was filled with argon gas.After the temperature programming to 800 ℃, gas is converted to the gaseous mixture of methane and hydrogen, volume ratio is 1: 20, and flow is 300sccm, and constant temperature carried out chemical vapour deposition (CVD) in 20 minutes.Then gas is converted to argon gas, naturally cools to room temperature and namely obtain silicon/carbon nano tube compound material, product 11.2 grams are denoted as C1.
Embodiment 4-6
Embodiment 4-6 is for the preparation of lithium ion battery of the present invention.
The preparation of negative pole
The negative electrode active material that respectively embodiment 1-3 is made, SBR, CMC and water were with 100: 2.5: 1.5: 120 weight ratio is mixed, and makes cathode size, and cathode size is uniformly coated on the copper foil surface that thickness is 10 μ m, and dry rear calendering obtains negative plate.
Anodal preparation
LiCoO with 100 grams
2Powder and as acetylene black 3 gram of conductive agent is blended in the 50 gram nmp solutions that contain 2 gram PVDF binding agents, is modulated into the anode mixture slurry.Above-mentioned anode mixture slurry is coated on the aluminium foil as collector body, rolls after dry.
The preparation of electrolyte
Ethylene carbonate and diethyl carbonate are mixed as solvent with 3: 7 volume ratios, with respect to this solvent with 1 mol/L with LiPF
6Electrolyte is made in dissolving.With respect to these electrolyte 100 weight portions, mix the vinylene carbonate of 5 weight portions, the electrolyte of using as battery.
The preparation of battery
The above negative pole that makes, positive pole, electrolyte and aluminium lamination shell are prepared into 053450 rectangular cell, are denoted as A1, A2 and A3, the active material of used negative pole is respectively embodiment 1,2 and 3 composite materials that make.
Comparative Examples 2
Make battery B1 according to the method identical with embodiment 4-6, different is that the composite material that use Comparative Examples 1 is made is as negative active core-shell material.
Performance test
Measure in accordance with the following methods first irreversible specific capacity, specific capacity and the cycle performance of lithium ion battery A1, A2, A3 and B 1.
Irreversible specific capacity first: under 25 ℃ with battery with 1C electric current constant current charge to 3.8V, then turn the constant voltage charging, cut-off current 0.05C; Then, again with battery with 1C electric current constant-current discharge to 2.75V, the difference of its initial charge specific capacity and first discharge specific capacity i.e. irreversible specific capacity first.
Specific capacity: under 25 ℃ with battery with 1C electric current constant current charge to 3.8V, then turn constant voltage charging, cut-off current 0.05C; Then, again with battery with 1C electric current constant-current discharge to 2.75V, obtain battery normal temperature 1C current discharge to the specific capacity of 2.75V.
Cycle performance: under the room temperature, with battery with 1C electric current constant current charge to 3.8V, then turn constant voltage charging, cut-off current 0.05C; Then, again with battery with 1C electric current constant-current discharge to 2.75V.Repeat above step 100 time, obtain after 100 circulations of battery normal temperature the 1C current discharge to the capacity of 2.75V, battery capacity sustainment rate after the computation cycles.
Measurement result is as shown in table 1.
Table 1
| Numbering | Irreversible specific capacity/mAh/g first | Specific capacity/mAh/g | Capability retention (%) |
| A1 | 700 | 1000 | 40 |
| A2 | 700 | 1080 | 60 |
| A3 | 550 | 850 | 55 |
| B1 | 2534 | 829 | 5 |
Can find out by table 1, the battery made from the negative pole of composite material provided by the invention preparation has lower first irreversible specific capacity, higher specific capacity and excellent cycle performance.
Claims (6)
1. the preparation method of a Si-C composite material is characterized in that, the method comprises nano-silicon and carbon nanotube dispersed in dispersant, removes dispersant, obtains nano-silicon/carbon nano-tube composite particles; Nano-silicon/carbon nano-tube composite particles is contacted with the amorphous carbon precursor solution, desolventizing, and make the charing of amorphous carbon presoma, wherein, the consumption of described nano-silicon, carbon nano-tube and amorphous carbon presoma makes in the composite material that obtains, take the nano-silicon of 100 weight portions as benchmark, the content of carbon nano-tube is the 1-25 weight portion, and the content of amorphous carbon is the 40-150 weight portion.
2. method according to claim 1, wherein, described amorphous carbon precursor solution is dissolved in the solvent by the amorphous carbon presoma and forms; Described amorphous carbon presoma is selected from one or more in resin, pitch, glucose, sucrose, starch, asccharin, benzene, naphthalene and the benzene naphthalene copolymer; The used solvent of amorphous carbon precursor solution is one or more in acetone, absolute ethyl alcohol, 1-METHYLPYRROLIDONE, chloroform and the cyclohexane; Take the 100 amorphous carbon presomas that restrain as benchmark, the addition of solvent is the 150-3000 milliliter.
3. method according to claim 1, wherein, the method for described desolventizing is dried under inert gas shielding for the nano-silicon that will be coated with the amorphous carbon precursor solution/carbon nano-tube composite particles, and bake out temperature is 200-400 ℃; The method of described charing is that the product after the desolventizing was kept 2-8 hour under 850-1200 ℃ under inert gas shielding.
4. method according to claim 3, wherein, described inert gas is selected from one or more in nitrogen and the group 0 element gas.
5. method according to claim 1, wherein, described dispersant is selected from one or more in water, ethanol, propyl alcohol, the propylene glycol; The consumption of described dispersant is that per 100 gram nano-silicons adding 1-15 rise dispersant.
6. method according to claim 1, wherein, the particle diameter of described nano-silicon is the 20-100 nanometer; The diameter of described carbon nano-tube is the 20-100 nanometer, and length is the 0.5-2 micron.
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