CN104025348B - Cathode active material, its preparation method and comprise its lithium secondary battery - Google Patents
Cathode active material, its preparation method and comprise its lithium secondary battery Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title description 18
- 239000006182 cathode active material Substances 0.000 title description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 151
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 121
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 107
- 239000010703 silicon Substances 0.000 claims abstract description 106
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 106
- 239000002070 nanowire Substances 0.000 claims abstract description 92
- 239000002245 particle Substances 0.000 claims abstract description 88
- 238000000576 coating method Methods 0.000 claims abstract description 53
- 239000011248 coating agent Substances 0.000 claims abstract description 49
- 239000011258 core-shell material Substances 0.000 claims abstract description 41
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- 239000010439 graphite Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
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Abstract
The present invention provides a kind of negative active core-shell material and the method preparing described negative active core-shell material, and described negative active core-shell material comprises carbon based particles, the carbon nanocoils grown in described carbon based particles and the carbon coating on the surface of described carbon based particles and described silicon nanowires.Because the negative active core-shell material of the present invention is in lithium secondary battery, so being possible not only to the physical bond power increasing between described carbon based particles and described silicon nanowires, and electric conductivity can be improved.Therefore, it can improve the life characteristic of described battery.
Description
Technical field
The present invention relates to cathode active material and preparation method thereof, and relate more particularly to comprise carbon back
Particle, in described carbon based particles growth silicon nanowires and on the surface of described carbon based particles and described silicon nanowires
The negative active core-shell material of carbon coating with and preparation method thereof.
Background technology
Recently, according to the miniaturization of electronic installation of the development according to information and telecommunications industry, lightness, slimming and just
Taking trend, for as the high energy density cells of the power supply of these electronic installations need increase.Currently, the most actively carry out
Research for the lithium secondary battery as the battery that may meet above-mentioned needs best.
By can embed/the various carbon-based materials including Delanium, native graphite or hard carbon of deintercalate lithium ions use
Make the negative active core-shell material of lithium secondary battery.In above-mentioned carbon-based material, graphite is most widely used, because it can be at lithium
The energy density aspect of battery provides advantage and can ensure that the long-life of lithium secondary battery due to the reversibility of its excellence.
But, because graphite is likely to be of low capacity in terms of the energy density of unit volume electrode, and at height electric discharge electricity
Pressure may promote the side reaction with organic electrolyte, causes burning it is possible that exist due to fault and the overcharge of battery
Or the danger of blast.
Therefore, Metal Substrate negative active core-shell material, such as silicon (Si) are had studied.Known silicon Metal Substrate negative active core-shell material
Show the high lithium capacity of about 4,200mAh/g.But, before and after reacting with lithium, i.e. it may happen that maximum 300% during discharge and recharge
Above change in volume.As a result, there is following phenomenon: the performance of battery may deteriorate, because the conductive network in electrode may
Damaged and interparticle contact resistance may increase.
Therefore, have attempted to following methods: wherein diameter according to the significant change of change in volume by the chi by silicon particle
Very little it be reduced to nanoscale from typical micron-scale and reduce.But, synthesizing uniform nano-silicon negative active core-shell material and inciting somebody to action
This nano-silicon negative active core-shell material is evenly distributed in the method in serosity and there may be many difficulties.
In order to solve these difficulties, along with the high-performance nano device such as field effect starting to realize using one-dimensional nano line is brilliant
Body pipe, photodetector, chemical sensor and biosensor, nano laser and light emitting diode (LED), except CNT
Outside, nano wire receives publicity as closest to business-like nano material.
As the example of this technology, have been developed for the silicon by injecting gaseous state and apply high heat and form nano wire
Method or the method that grows nano wire by directly heating silicon chip.But, in these cases, the performance of battery may be by
Contact with light current in the disengaging of silicon nanowires during serosity preparation or battery operation and deteriorate.
Therefore, in the urgent need to being developed for solving the negative active core-shell material of above-mentioned restriction.
Summary of the invention
Technical problem
The present invention provides can be by increasing between carbon based particles and the silicon nanowires grown in described carbon based particles
Physical bond power and improve electric conductivity and improve the negative active core-shell material of the performance of secondary cell with and preparation method thereof.
Technical scheme
According to an aspect of the present invention, it is provided that a kind of negative active core-shell material, it comprises carbon based particles, in described carbon based particles
The silicon nanowires of upper growth and the carbon coating formed on the surface of described carbon based particles and described silicon nanowires.
According to a further aspect in the invention, it is provided that a kind of method preparing negative active core-shell material, it includes by using silicon
Raw material and catalytic metal and in carbon based particles, grow silicon nanowires；And have described at described silicon nanowires and growth thereon
Carbon coating is formed on the surface of the described carbon based particles of silicon nanowires.
According to a further aspect in the invention, it is provided that a kind of negative pole, its comprise current collector and at described current collector at least one
The described negative active core-shell material formed on individual surface.
According to a further aspect in the invention, it is provided that a kind of lithium secondary battery, it comprises positive pole, described negative pole and is arranged on
Barrier film between described positive pole and described negative pole.
Advantageous effects
Because by wherein in carbon based particles with in described carbon based particles, on the surface of the silicon nanowires of growth, formation carbon is coated with
The negative active core-shell material of the present invention of layer, in lithium secondary battery, so being possible not only to improve electric conductivity, and can enter one
Step increases the physical bond power between carbon based particles and silicon nanowires.Therefore, it can improve the life characteristic of described battery.
Accompanying drawing explanation
Appended by this specification with the exemplified preferred embodiment of the present invention of figure below, and and detailed description given below
Together for making it possible to be further appreciated by the technical concept of the present invention, and therefore, the present invention should be only with in these figures
Content is explained.
Fig. 1 is the schematic diagram illustrating the negative active core-shell material according to an embodiment of the invention；
Fig. 2 and Fig. 3 is the scanning electron microscope of the negative active core-shell material prepared in comparative example 1 and embodiment 1 respectively
(SEM) image；
Fig. 4 and Fig. 5 be for determine respectively by the negative active core-shell material of comparative example 1 and embodiment 1 in water, ethanol and first
The SEM image of the residual degree of silicon nanowires after dilution in benzene；
Fig. 6 is the figure of the discharge capacity of the lithium secondary battery illustrating embodiment 2 and comparative example 2；And
Fig. 7 is the figure of the coulombic efficiency of the lithium secondary battery illustrating embodiment 2 and comparative example 2.
Detailed description of the invention
Hereinafter, the present invention be will be described in further detail so that being more clearly understood that the present invention.
Should be understood that and the word used in the present specification and claims or term are not construed in everyday words
Implication defined in allusion quotation.Will be further understood that the implication that can suitably limit word or term based on the present inventor
To explain the principle of the present invention best, it is construed to word or term to have with them in the correlation technique of the present invention and technology
The implication that implication in the background of thought is consistent.
The cathode active material of the present invention can comprise carbon based particles；Described carbon based particles grows
Silicon nanowires；And on the surface of described carbon based particles and described silicon nanowires formed carbon coating.
According to an embodiment of the invention, the change in volume produced during discharge and recharge can be by carbon based particles
Upper direct growth silicon nanowires suppresses.It addition, because can be by forming carbon on the surface of carbon based particles and silicon nanowires
Coating increases the adhesion between described silicon nanowires and described carbon based particles further, it is possible to prevent silicon nanowires
Depart from, and the performance of battery can be improved further by providing electric conductivity.
Specifically, the schematic diagram of negative active core-shell material as shown in Figure 1, bearing according to an embodiment of the invention
Pole active material may be embodied in the silicon nanowires 11 of growth in carbon based particles 12 and in silicon nanowires 11 and carbon based particles 12
Surface on formed carbon coating 13.
According to an embodiment of the invention, can be by coating carbon based particles 12 and silicon nanowires partially or completely
The surface of 11 forms carbon coating 13.But, because being formed by all surfaces of coating carbon based particles 12 and silicon nanowires 11
Carbon coating 13 can increase the adhesion between silicon nanowires 11 and carbon based particles 12 further, thus prevents silicon nanowires 11 from taking off
From, it is possible to improve the performance of secondary cell.
Can will can embed or the material with carbon element of deintercalate lithium ions is used as the carbon back that uses in embodiments of the present invention
Particle.Described carbon based particles can comprise any one in carbon-based powder, white carbon black, native graphite and Delanium or its
Two or more mixture.Described carbon based particles can have the mean diameter (D of 10 μm～30 μm50)、2.0m2/ g～5.0m2/
The specific surface area of g and the pressed density of 1.5g/cc～1.85g/cc under the pressure of 12mpa～16mpa.
In the present invention, the mean diameter (D of described carbon particle50) can be defined as at the 50% of accumulation particle diameter distribution
Particle diameter.Such as, according to the mean diameter (D of the carbon particle of an embodiment of the invention50) can be by using laser diffraction
Method is measured.Described laser diffractometry generally can be measured the particle diameter of pattern of sub-micron level to several millimeters and can obtain and can highly repeat
And high-resolution result.
It addition, the specific surface area of described carbon based particles can be by the special Teller (Brunauer-of mono-angstrom of prunus mume (sieb.) sieb.et zucc. of Bu Lunuo
Emmett-Teller) (BET) method is measured.Such as, described specific surface area can be used according to nitrogen adsorption methods by 6 BET method
Lacunarity analysis instrument (Belsorp-II mini is manufactured by Bell Japan Inc.) is measured.
Silicon nanowires according to an embodiment of the invention can be to comprise the diameter and height having in nanometer range
The concept of the silicon of the linear formula of aspect ratio uses and unrelated with its preparation method.Therefore, in the concept of described silicon nanowires
In can comprise silicon nanorod or nano-tube.
According to an embodiment of the invention, there is the described carbon based particles of described silicon nanowires based on growth thereon
Gross weight, in described silicon nanowires, the amount of silicon can be in the range of 5 weight %～30 weight %.Amount at silicon is more than above-mentioned scope
In the case of, because the silicon of excess covers described carbon based particles, so specific surface area can increase, thus promote dividing of electrolyte
Solve reaction.In the case of the amount of silicon is less than above-mentioned scope, receive because silicon may not be grown in described carbon based particles completely
Rice noodle, so the life characteristic of secondary cell may deterioration.
Silicon nanowires according to embodiment of the present invention can have about 10nm～the diameter of about 100nm and about 100nm～
The length of about 5 μm.It addition, described nano wire can be linearly or nonlinearly, wherein said nano wire can its all or
Bending or tortuous on partial-length.Generally, although silicon (Si) shows high lithium capacity, but Si is before and after reacting with lithium, i.e. in charge and discharge
The change in volume of more than 300% may be caused during electricity.Described change in volume can be grown by Direct Three-dimensional in carbon based particles
Nano wire eliminates.
But, during growth has the carbon based particles of nano wire thereon, the life-span of battery is likely to be due at serosity preparation or electricity
When during the operation of pond, adhesion between nano wire with carbon based particles is low, disengaging and the light current of silicon nanowires contact and reduce.
Because forming carbon coating on the silicon nanowires of growth and the surface of described carbon based particles in carbon based particles, so
Other electric conductivity can be provided, and the combination between carbon based particles and silicon nanowires can be strengthened to prevent according to filling simultaneously
During the change in volume of electric discharge, silicon nanowires departs from from carbon based particles.Therefore, the present invention can provide the excellent longevity of secondary cell
Life characteristic and charge/discharge capacity characteristic.
It addition, in negative active core-shell material according to the embodiment of the present invention, the thickness of described carbon coating can be at 5nm
～in the range of 50nm.In the case of the thickness of carbon coating is less than 5nm, carbon coating the effect that the electrical conductivity caused increases can
Being inessential and may be high with the reactivity of electrolyte during coating negative active core-shell material.Accordingly, it is possible at the beginning of Jiang Diing
Beginning efficiency.In the case of the thickness of carbon coating is more than 50nm, because the thickness of carbon coating may excessively increase, thus serve as lithium
The barrier of ion migration, therefore resistance may increase.
By the method preparing negative active core-shell material according to an embodiment of the invention detailed further below:
It is to say, the method preparing negative active core-shell material according to the embodiment of the present invention may include that by making
In carbon based particles, silicon nanowires (step i) is grown with silicon raw material and catalytic metal；And at described silicon nanowires with at it
Upper growth has formation carbon coating (step ii) on the surface of the described carbon based particles of described silicon nanowires.
According to an embodiment of the invention growth silicon nanowires (in step i), growth silicon nanowires method
Can be typical method as known in the art, and can be such as selected from gas-liquid-solid phase (VLS) Gu method, solid-liquid-(SLS)
Method, metal organic chemical vapor deposition (MOCVD) method and the method for molecular beam epitaxy (MBE) method.Such as, described growth silicon nanometer
The method of line can be VLS method.
SiCl can be comprised for growing the silicon raw material of described silicon nanowires4、SiH4Or its mixture.
Described catalytic metal can be the crystal seed of growth nanostructured, and can be the shape of metallic film or metal dust
Formula.Described metallic film such as can have about～about 1, the thickness of 000nm, and described metal dust such as can have
The diameter of 1nm～1,000nm.But, the present invention is not limited especially by this.The one of described catalytic metal can comprise and can subtract
The metal of the fusing point of little silicon.The example of described catalytic metal can include in gold (Au), ferrum (Fe), silver (Ag) and nickel (Ni)
Any one or its two or more hybrid metal.
It addition, in order to there be the carbon based particles of silicon nanowires provide surface conductivity and strengthen at described silicon to growth thereon
Physical bond power between nano wire and described carbon based particles, can grow the described carbon back grain having described silicon nanowires thereon
Carbon coating (step ii) is formed on the surface of son.
According to an embodiment of the invention, described carbon coating can be by having grown with the coating of carbon precursor thereon
State the described carbon based particles of silicon nanowires and carry out heat treatment and formed.
Any carbon precursor can be used not limit, as long as it can form carbon, and such as institute by heat treatment
State carbon precursor and can comprise the gas containing carbon or amorphous carbon.Specifically, described amorphous carbon can comprise selected from following any one
Or its two or more mixture: glucose, fructose, galactose, maltose, lactose, sucrose, phenol resin, naphthalene resin, poly-
Vinyl alcohol resin, polyurethane resin, polyimide resin, furane resins, celluosic resin, epoxy resin, polystyrene resin,
Colophonium, the Colophonium of petroleum derivation and the tar that resin based on resorcinol, resin based on phloroglucinol, coal are derivative.
According to an embodiment of the invention, the Colophonium at the Colophonium that coal is derivative or petroleum derivation is used as described amorphous
In the case of carbon, the weight average molecular weight (Mw) of described Colophonium can be 200～3, in the range of 000.Weight-average molecular when Colophonium
When amount is more than 3,000, the dispersion of solvent may be difficult, and therefore may not carry out uniform Colophonium coating.Weight when Colophonium
When average molecular weight is less than 200, the yield during described Colophonium is coated with may reduce and be likely difficult to obtain uniform coating.Separately
Outward, in order to carry out even spread by making Colophonium penetrate into the gap between silicon nanowires, the weight average molecular weight of described Colophonium
Can be 400～1, in the range of 500, more preferably in the range of 500～800.
Additionally, according to an embodiment of the invention, growth thereon has the described carbon based particles of described silicon nanowires
To the mixing ratio of described carbon precursor (such as, amorphous carbon) at 90 weight portions: 10 weight portions～99 weight portions: the scope of 1 weight portion
In, more preferably at 90 weight portions: 10 weight portions～95 weight portions: in the range of 5 weight portions.Weight at carbon precursor is less than 1 weight
In the case of amount part, because total coating weight is not enough, so not only combination between described carbon based particles and described silicon nanowires
Power may reduce, and is likely to be difficult to obtain uniform coating.In the case of the weight of carbon precursor is more than 10 weight portions, powder
End is likely to be due to aggregation of particles after carburization and condenses.
Such as, the method that described amorphous carbon precursor carburizing can be used in described coating.Can be by dry type or wet type
Rubbing method is used as described coating process.Further, it is possible to use utilize gas such as methane, ethane, propane, ethylene and second containing carbon
The deposition process of alkynes such as chemical vapor deposition (CVD) method forms described carbon coating.
According to an embodiment of the invention, described wet coating method such as can by will grow thereon have described
The described carbon based particles of silicon nanowires is immersed in wherein dilution and carries out in having the organic solvent of amorphous carbon.According to the present invention's
In the case of embodiment uses wet, by non-with described for the described carbon based particles that growth thereon has described silicon nanowires
Brilliant carbon such as mixes with blender or mortar, and subsequently by the mixture thus prepared is immersed in solvent, i.e. selected from ethanol,
Any one in toluene, methanol, hexane, acetone, oxolane, pyridine, quinoline and benzoquinone or its two or more mixture
In carry out wet.Subsequently, heat treatment can be carried out.
According to an embodiment of the invention, described heat treatment can be carried out in an inert atmosphere.Described heat treatment exists
Carry out at a temperature of 300 DEG C～1,500 DEG C and can be at a temperature of preferably 300 DEG C～800 DEG C, more preferably 300 DEG C～500 DEG C
Carry out 5 hours～10 hours.In the case of the temperature of described heat treatment is less than 300 DEG C, because the organic of remnants may be remained
Or inorganic material, so the resistance of described coating may increase.It addition, because desired solid electrolyte circle may not be formed
Face (SEI) layer, it is possible that reduce the starting efficiency relevant with battery performance.Temperature at described heat treatment is more than 1,500 DEG C
In the case of, processing cost may increase.
Described carbon based particles and described silicon nanowires completely homogeneously or can be coated with unevenly with described carbon coating, and
Described carbon coating can be formed to cover part or all of described carbon based particles and described silicon nanowires.Described coating
Thickness be not particularly limited.But, its thickness can be in the range of 5nm～50nm, preferably in the scope of 5nm～20nm
In.
It addition, the present invention can comprise a kind of negative pole, described negative pole comprises current collector and is formed at described current collector extremely
Described negative active core-shell material on a few surface.
According to an embodiment of the invention, described negative pole can pass through the most normally used preparation method
Prepare.It addition, similar with described negative pole, according to an embodiment of the invention, positive pole can be by the allusion quotation in this area
Prepared by type method.
Such as, if by the positive electrode active materials of the present invention and negative active core-shell material and binding agent, solvent and conductive agent and
Necessary dispersant, and stir to prepare serosity.Subsequently, current collector can be coated with and suppresses with described serosity with preparation
Electrode.
Can by various binder polymers such as polyvinylidene fluoride-hexafluoropropylene copolymer (the co-HEP of PVDF-), poly-partially
Difluoroethylene, polyacrylonitrile and polymethyl methacrylate are used as the binding agent used in the present invention.
Transition metal oxide containing lithium can be used as positive electrode active materials.It is, for example possible to use appoint selected from following
A kind of or that they are two or more mixture: LixCoO2(0.5<x<1.3)、LixNiO2(0.5<x<1.3)、LixMnO2(0.5<x<
1.3)、LixMn2O4(0.5<x<1.3)、Lix(NiaCobMnc)O2(0.5<x<1.3,0<a<1,0<b<1,0<c<1,a+b+c=1)、
LixNi1-yCoyO2(0.5<x<1.3,0<y<1)、LixCo1-yMnyO2(0.5<x<1.3,0≤y<1)、LixNi1-yMnyO2(0.5<x<
1.3,0≤y<1)、Lix(NiaCobMnc)O4(0.5<x<1.3,0<a<2,0<b<2,0<c<2,a+b+c=2)、LixMn2-zNizO4
(0.5<x<1.3,0<z<2)、LixMn2-zCozO4(0.5<x<1.3,0<z<2)、LixCoPO4(0.5 < x < 1.3) and LixFePO4
(0.5<x<1.3).The described transition metal oxide containing lithium can be with metal such as aluminum (Al) or metal oxide coated.It addition,
In addition to the described transition metal oxide containing lithium, it is also possible to use sulfide, selenides and halogenide.
When preparing described electrode, it is possible to use described electrode is prepared to comprise and is generally used in this area and is arranged on institute
State the lithium secondary battery of the barrier film between positive pole and described negative pole and electrolyte.
In the electrolyte used in the present invention, it is possible to use can as the lithium salts that electrolyte comprises can and do not limit
System, as long as it generally uses in electrolyte for lithium secondary batteries.It is, for example possible to use selected from any one following conduct
The anion of described lithium salts: F-、Cl-、Br-、I-、NO3 -、N(CN)2 -、BF4 -、ClO4 -、PF6 -、(CF3)2PF4 -、(CF3)3PF3 -、
(CF3)4PF2 -、(CF3)5PF-、(CF3)6P-、CF3SO3 -、CF3CF2SO3-、(CF3SO2)2N-、(FSO2)2N-、CF3CF2(CF3)2CO-、(CF3SO2)2CH-、(SF5)3C-、(CF3SO2)3C-、CF3(CF2)7SO3 -、CF3CO2 -、CH3CO2 -、SCN-(CF3CF2SO2)2N-。
In the electrolyte used in the present invention, it is possible to use the organic solvent that comprises in electrolyte and do not limit, only
In electrolyte for lithium secondary batteries to be commonly used for.Typically, it is possible to use selected from following any one or its two
Kind above mixture: propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC),
Ethyl methyl carbonate (EMC), methyl propyl carbonate, dipropyl carbonate, dimethyl sulfoxide, acetonitrile, dimethoxy-ethane, diethoxy second
Alkane, vinylene carbonate, sulfolane, gamma-butyrolacton, sulfurous acid Asia propyl ester and oxolane.Especially, carbonate group is organic molten
Ring-like carbonic ester in agent, ethylene carbonate and propylene carbonate, due to the high-k as high-viscosity organic solvent
The fully lithium salts in dissociation electrolyte, and therefore can use described ring-like carbonic ester.Because by described ring-like carbonic ester with
Low viscosity, the linear carbonates such as dimethyl carbonate and diethyl carbonate of low-k can be prepared when mixing with adequate rate
There is the electrolyte of high conductivity, it is possible to use the most described ring-like carbonic ester.
Optionally, the additive comprised can be also included in typical case's electrolyte such as according to the electrolyte of the storage of the present invention
Overcharge inhibitor.
The typical porous polymer film used as exemplary septum, such as by polyolefin based polymer such as ethylene homo
Prepared by thing, Noblen, ethylene/butylene copolymers, ethylene/hexene copolymer and ethylene/methacrylic acid ester copolymer
Porous polymer film individually or can be used as barrier film with its layered product.Further, it is possible to use typical perforated nonwoven fabrics,
The non-woven fabrics such as formed by high melting glass fiber or pet fiber.But, barrier film is not limited
System.
The shape of the lithium secondary battery of the present invention is not particularly limited, and such as can use: use the column type of tank, rib
Column type, pouch-type or Coin shape.
Hereinafter, the present invention will be described in detail according to specific embodiment.But, the present invention can be with many not similar shapes
Formula is implemented and should not be construed as limited to embodiment described in this paper.And be to provide these illustrative embodiment from
And make this specification thorough and complete, and those skilled in the art will be given full expression to the scope of present inventive concept.
Embodiment
Hereinafter, the present invention will be more fully described according to embodiment and experimental example.But, the present invention is also not limited
System.
<preparation of negative active core-shell material>
Embodiment 1
Gold (Au) is arranged on the mean diameter (D with about 20 μm50) graphite particle on and graphite particle and Au put
In batch-type reactor.The temperature of this reactor is maintained at about 400 DEG C and subsequently by use argon (Ar) as
Carrier gas is as the SiH of reacting gas4While carry out VLS reaction.As a result, on graphite particle growth have 10nm～
The diameter of 100nm and the silicon nanowires of the length of 2 μm.The weight of silicon nanowires can control according to the response time.In this reality
Executing in example, graphite is 92 weight %:8 weight % to the weight ratio of silicon nanowires.
By having the graphite of silicon nanowires to be immersed in the ethanol (6 of the Colophonium that wherein dilution has coal to derive growth thereon
Weight % Colophonium-ethanol solution) in carry out wet, and at 400 DEG C, in argon atmospher, carry out heat treatment subsequently with preparation
Comprise growth thereon and have the negative active core-shell material of the carbon coating on the graphite of silicon nanowires and the surface of silicon nanowires.
Comparative example 1
Preparing negative active core-shell material in the same manner as in example 1, difference is to grow thereon has silicon to receive
It is formed without carbon coating on the graphite particle of rice noodle.Graphite is 92 weight %:8 weight % to the weight ratio of silicon nanowires.
<preparation of lithium secondary battery>
Embodiment 2
Using the negative active core-shell material prepared in embodiment 1, as the butadiene-styrene rubber (SBR) of binding agent, as thickening agent
Carboxymethyl cellulose (CMC) and mix with the weight ratio of 95:2:2:1 as the acetylene black of conductive agent and will thus obtained mix
Compound mixes with the water as solvent to prepare uniform negative pole serosity.By copper collector surface with prepared negative pole
Serosity is applied to the thickness of 65 μm, is dried and rolls.Prepare negative pole by being stamped into preliminary dimension subsequently.
Ethylene carbonate (EC) and diethyl carbonate (DEC) are mixed with the volume ratio of 30:70, and by LiPF6Add to
To prepare 1M LiPF in the nonaqueous electrolyte solvent thus prepared6Nonaqueous electrolytic solution.
It addition, lithium paper tinsel is used as electrode, i.e. positive pole, polyalkene diaphragm is arranged between two electrodes, and leads to subsequently
Cross injection electrolyte to prepare Coin shape lithium secondary battery.
Comparative example 2
Preparing Coin shape lithium secondary battery in the way of in the same manner as in Example 2, difference is to use at comparative example 1
The negative active core-shell material of middle preparation.
Experimental example 1
<scanning electron microscope (SEM) image: determine that carbon coating is formed>
Sem analysis is carried out respectively to determine silicon nanowires on the negative active core-shell material of preparation in comparative example 1 and embodiment 1
Extent of growth, and its result is shown in Fig. 2 and Fig. 3.
Specifically, Fig. 2 (a)～2 (c) are shown in comparative example 1 negative pole not having carbon coating of preparation according to amplification
The SEM image on the surface of active material, and Fig. 3 (a) and Fig. 3 (b) illustrate that according to amplification for preparing in embodiment 1 comprises
The SEM image on the surface of the negative active core-shell material of carbon coating.
As shown in Figures 2 and 3, it may be determined that in embodiment 1 and comparative example 1, on graphite particle, growth has silicon nanometer
Line.Especially, as shown in Figure 3, it may be determined that on all graphite particles and silicon nanowires, all comprise carbon coating.
By contrast, when checking the high-amplification-factor image of Fig. 2 (c), it may be determined that in carbon based particles, growth has silicon
Nano wire, but it is formed without carbon coating.
Experimental example 2
<SEM image: determine the physical bond power between carbon based particles and silicon nanowires>
By in comparative example 1 and embodiment 1 preparation negative active core-shell material respectively in water, ethanol and toluene with 1g/mL
Dilute and stir 12 hours at 60 DEG C.Subsequently, determine, by SEM image, the degree that silicon nanowires remains in each solvent, and
The results are shown in Fig. 4 and Fig. 5.
As shown in Figure 4, about the comparative example 1 not having carbon coating, it may be determined that the rear portion silicon of dilution in water is received
Rice noodle departs from, and it may also be determined that major part silicon nanowires is from graphite particle disengaging in ethanol and toluene so that silicon nanowires
Almost do not remain on graphite particle.
By contrast, as shown in Figure 5, about the negative active core-shell material of embodiment 1, it may be determined that in water, toluene and second
In alcohol, silicon nanowires is combined with graphite particle and keeps intact.
It is, therefore, to be understood that the physical bond power between carbon based particles and silicon nanowires is by carbon based particles with at it
Comprise carbon coating on the silicon nanowires of upper growth and strengthen.
Experimental example 3
<cycle characteristics>
By using the charge-discharge machine (WBCS3000 is manufactured) the lithium secondary to embodiment 2 and comparative example 2 by WONA TECH
Cell evaluation charge-discharge characteristic.
By the lithium secondary battery (battery capacity: 3.4mAh) of preparation in embodiment 2 and comparative example 2 at the constant electricity of 0.1C
It is charged to the voltage of 10mV under stream (CC), thereafter through under constant voltage (CV), lithium secondary battery is charged to 0.17mAh's
Electric current carries out the charging of the first circulation.After making battery standing 10 minutes, by under the constant current of 0.1C by battery
The voltage discharging into 1V measures the discharge capacity in the first circulation.Subsequently, regarding to embodiment 2 and each battery of comparative example 2, weight
Multiple discharge and recharge 100 circulation is to measure the discharge capacity of each circulation.The results are shown in Fig. 6.
As shown in Figure 6, about comparative example 2, capacity reduces from the 50th circulation and is reduced to the 100th circulation
More than 50%.By contrast, about embodiment 2, it will be understood that until the 60th circulation volume has almost no change and the most straight
Also have almost no change to the 100th circulation volume.
It addition, as shown in Figure 7, about comparative example 2, coulombic efficiency increases along with period and reduces.By contrast, close
In embodiment 2, Initial Coulombic Efficiencies is similar with the Initial Coulombic Efficiencies of comparative example 2.But, coulombic efficiency increases along with period
And increase, and obtain the coulombic efficiency of up to 99.99% the 100th circulation.
This instruction, because prepared silicon nanowires does not damage due to carbon coating and keeps complete on graphite particle
Lossless, it is possible to improve the life-span of battery.
Industrial applicability
Because being possible not only to improve electric conductivity according to the negative active core-shell material of an embodiment of the invention, and permissible
Increase the physical bond power between carbon based particles and silicon nanowires further, it is possible to improve the life characteristic of secondary cell.
Therefore, described negative active core-shell material may adapt to secondary cell.
Claims (12)
1. a negative active core-shell material, it comprises:
Carbon based particles；
The silicon nanowires of growth in described carbon based particles；And
The carbon coating formed on the surface of described carbon based particles and described silicon nanowires,
Mean diameter D of wherein said carbon based particles50In the range of 10 μm～30 μm,
Described silicon nanowires has the diameter of 10nm～100nm and 100nm～the length of 5 μm,
Have the gross weight of the described carbon based particles of described silicon nanowires based on growth thereon, the amount of silicon is at 5 weight %～30 weights
In the range of amount %,
The thickness of described carbon coating in the range of 5nm～50nm,
Described carbon coating covers described carbon based particles and all surfaces of described silicon nanowires.
2. the negative active core-shell material of claim 1, wherein said carbon based particles comprises selected from white carbon black, native graphite and Delanium
In any one or its two or more mixture.
3. the negative active core-shell material of claim 1, the described carbon back grain wherein measured by the special Teller method of mono-angstrom of prunus mume (sieb.) sieb.et zucc. of Bu Lunuo
The specific surface area of son is at 2.0m2/ g～5.0m2In the range of/g, and described carbon based particles under the pressure of 12mpa～16mpa
Pressed density is in the range of 1.5g/cc～1.85g/cc.
4. the method preparing negative active core-shell material, described method includes:
By using silicon raw material and catalytic metal to grow silicon nanowires in carbon based particles；And
Described silicon nanowires and thereon growth have described silicon nanowires described carbon based particles surface on formed carbon coating
To cover described carbon based particles and all surfaces of described silicon nanowires,
Wherein said carbon coating is by having the described carbon based particles of described silicon nanowires with carbon precursor coating growth thereon and enter
Row heat treatment is formed,
The wet coating method that described coating dilutes carbon precursor in organic solvent by use is carried out,
Described carbon precursor comprises amorphous carbon,
Described amorphous carbon for having 400～15, Colophonium that the coal of the weight average molecular weight of 00 is derivative or the Colophonium of petroleum derivation,
Described organic solvent comprises in ethanol, toluene, methanol, hexane, acetone, oxolane, pyridine, quinoline and benzoquinone
Any one or its two or more mixture, and
Carry out described heat treatment in an inert atmosphere.
5. the method for claim 4, wherein said silicon nanowires grow through selected from gas-liquid-solid (VLS) Gu method, solid-liquid-
(SLS) method of method, metal organic chemical vapor deposition (MOCVD) method and molecular beam epitaxy (MBE) method is carried out.
6. the method for claim 4, wherein said silicon raw material comprises SiCl4、SiH4Or its mixture.
7. the method for claim 4, wherein said catalytic metal comprises in gold (Au), ferrum (Fe), silver (Ag) and nickel (Ni)
Any one or its two or more hybrid metal.
8. the method for claim 4, wherein said wet coating method is by having growth thereon described in described silicon nanowires
Carbon based particles is immersed in wherein dilution and carries out in having the organic solvent of carbon precursor.
9. the method for claim 4, growth the most thereon has the described carbon based particles of described silicon nanowires to described carbon precursor
Mixing ratio at 90 weight portions: 10 weight portions～99 weight portions: in the range of 1 weight portion.
10. the method for claim 4, wherein said heat treatment, at 300 DEG C～1, is carried out at a temperature of 500 DEG C.
11. 1 kinds of negative poles, it comprises the negative of current collector and the claim 1 that formed at least one surface of described current collector
Pole active material.
12. 1 kinds of lithium secondary batteries, it comprises positive pole, the negative pole of claim 11 and is arranged on described positive pole and described negative pole
Between barrier film.
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| Application Number | Priority Date | Filing Date | Title |
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| KR10-2012-0138524 | 2012-11-30 | ||
| KR20120138524 | 2012-11-30 | ||
| KR1020130145165A KR101557559B1 (en) | 2012-11-30 | 2013-11-27 | Anode active material for lithium secondary battery, preparation method thereof, and lithium secondary battery comprising the same |
| KR10-2013-0145165 | 2013-11-27 | ||
| PCT/KR2013/010919 WO2014084635A1 (en) | 2012-11-30 | 2013-11-28 | Anode material for lithium secondary battery, method for manufacturing same, and lithium secondary battery comprising same |
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| CN104025348A CN104025348A (en) | 2014-09-03 |
| CN104025348B true CN104025348B (en) | 2016-11-30 |
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| CN102428763A (en) * | 2009-05-19 | 2012-04-25 | 纳米***公司 | Nanostructured materials for battery applications |
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| CN102428763A (en) * | 2009-05-19 | 2012-04-25 | 纳米***公司 | Nanostructured materials for battery applications |
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Effective date of registration: 20211129 Address after: Seoul, South Kerean Patentee after: LG Energy Solution,Ltd. Address before: Seoul, South Kerean Patentee before: LG CHEM, Ltd. |