CN106328887A - Anode material of lithium ion battery and preparation method thereof - Google Patents
Anode material of lithium ion battery and preparation method thereof Download PDFInfo
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- CN106328887A CN106328887A CN201510342874.XA CN201510342874A CN106328887A CN 106328887 A CN106328887 A CN 106328887A CN 201510342874 A CN201510342874 A CN 201510342874A CN 106328887 A CN106328887 A CN 106328887A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention discloses a lithium ion battery anode material and a preparation method thereof. The anode material of the lithium ion battery comprises nano silicon monoxide, graphite and an amorphous carbon coating layer; the nano silicon oxide particles are embedded or wrapped in the graphite, and the amorphous carbon coating layer covers the outer surface of the graphite. The preparation method is a method for preparing the anode material by utilizing a high-speed dispersion mixer and a mechanical fusion machine. Compared with the prior art, the battery prepared by using the anode material of the lithium ion battery has the advantages of excellent cycle performance, small cell expansion and the like, and is very suitable for consumer electronic products; the method has the advantages of simple process, environmental friendliness and suitability for large-scale mass production.
Description
Technical field
The invention belongs to field of lithium ion battery, it is more particularly related to a kind of cycle performance is excellent
Lithium ion battery anode material and preparation method thereof.
Background technology
Along with electronic equipment is to portable and miniaturization development, it is widely used in business-like graphite at present
Specific discharge capacity is played to the limit, and due to the limitation of intrinsic, graphite cannot meet lithium ion battery
Demand to higher energy density.In this context, sight is gradually proceeded to the silicon material of high storage lithium by people
On material.The theoretical gram volume of silicon materials is up to 4200mAh/g, for more than ten times of graphite, but, it causes
The weakness of life is exactly during removal lithium embedded, and change in volume is up to more than 300%, and this leverages material originally
The stability of body and be prepared as the availability after battery, has the most just had a strong impact on and has made its business-like paces.
In order to change above-mentioned condition, scientific research personnel has to take the second best, and on the premise of loss gram volume, passes through
Alloying reduces the volumetric expansion of silicon materials；Nowadays by making great efforts untiringly, industry generally believe have most uncommon
It is silicon monoxide that prestige is applied to business-like aluminosilicate alloy material.The reversible capacity of silicon monoxide is about
1400mAh/g, according to the current gram volume requirement to lithium ion battery anode material, prior art is substantially
It is simply mixed by a certain percentage with graphite and uses.But, although the volumetric expansion of silicon monoxide is relative
Much smaller in pure silicon material, the biggest, due to the oxygen after being simply mixed with graphite relative to graphite
SiClx the most still directly can contact with electrolyte, therefore its volume produced in continuous cyclic process
Expand and the SEI film causing granule outer layer is ceaselessly crushed and produces new interface；Along with the carrying out of discharge and recharge,
Fresh surfaces needs again to consume electrolyte to form new SEI；So circulation is gone down, and not only causes a large amount of electricity
Solve the repeat consumption of liquid, but also at the by-product of silicon monoxide surface deposition increasingly thickness, thus can cause
Lithium ion diffusion difficulty, poor electric contact between granule；Under the effect of factor the most in many ways, the circulation of battery
Life-span is considerably reduced.
The key of solution the problems referred to above is that avoids silicon monoxide directly to contact with electrolyte, protects again simultaneously
The volumetric expansion of card silicon monoxide intrinsic does not interferes with the expansion that electrode is overall.To this end, it has been proposed that use
Chemical organic solvent dispersion nano-silicon, it is intended to realize being scattered in graphite granule gap silicon nanoparticle, system
For going out Si/C composite；But, the material that the method prepares, more silicon nanoparticle is only
Be attached to the surface of graphite granule, and be not placed in inside granule, the most do not change silicon with
The situation that electrolyte directly contacts, the improvement for battery cycle life is also the most very limited；It addition, it is a large amount of
Organic solvent is used also to make product treatment complicate, the most unfriendly to environment, it is unfavorable for realizing extensive life
Produce.Somebody proposes to use ball-milling method to be embedded in graphite gaps by Si or SiO, but this technique there is also
The biggest drawback: first, is directly placed at graphite and nano silicon material in ball mill and carries out high-energy ball milling, ball
The existence of grinding media such as zirconium pearl, can inevitably induce one in raw material (graphite and silicon alloy) exotic
Matter, the most also can make graphite granule again be pulverized and attenuate, and causes it cannot provide enough for silicon alloy
Accommodate space；Furthermore, owing to silicon alloy is the powder of Nano grade, it is easy to occur in mechanical milling process
Reuniting, also would not be uniformly distributed in the internal void of graphite granule, this influences whether prepared sun undoubtedly
The chemical property of pole material.
In view of this, necessary offer a kind of can by silicon monoxide Particles dispersed method in graphite,
And use the method to prepare the lithium ion battery anode material that a kind of cycle performance is excellent.
Summary of the invention
It is an object of the invention to: provide a kind of can by silicon monoxide Particles dispersed method in graphite,
To avoid silicon monoxide directly to contact with electrolyte, thus overcome because silicon monoxide intrinsic volumetric expansion brings
Electrode expansion, reaches to be effectively improved battery core deformation, the purpose of prolongation battery cycle life；Another of the present invention
Purpose is to provide lithium ion battery anode material that said method is prepared, that have excellent cycling performance.
In order to realize foregoing invention purpose, the invention provides a kind of lithium ion battery anode material preparation method,
It comprises the following steps:
1) nanometer silicon monoxide and graphite are positioned over mix homogeneously in high speed dispersion mixer；
2) being transferred to mixture in mechanical fusion machine merge grind, grinding frequency is 2000～6000r/min,
Milling time is 10～60min, obtains the presoma first of graphite parcel nanometer silicon monoxide；
3) will mix homogeneously during presoma and organic polymer are positioned over high speed dispersion mixer first, the most again
Proceed in mechanical fusion machine, under 2000～6000r/min frequencies, grind 10～60min, obtain secondary presoma；
4) secondary presoma is placed in high-temperature rotary furnace, under inert gas shielding, Pintsch process carbonization,
Obtain lithium ion battery anode material.
Described step 2) in milling time more than 10min, frequency more than 2000r/min, be because only existing
Nanometer silicon monoxide just can be made under this precondition to be completely embedded in artificial spherical graphite or by natural flake stone
Ink parcel；If but the time is more than 6000r/min more than 30min, frequency, then graphite granule surface is broken
Badly can aggravate, will also result in unnecessary energy consumption simultaneously.
Compared with prior art, lithium ion battery anode material preparation method not only technique of the present invention is simple, and
And environmental friendliness, survivable graphite granule, also will not introduce foreign substance, scale of mass production can be realized.
As a kind of improvement of lithium ion battery anode material preparation method of the present invention, described step 1) or 3)
Incorporation time be preferably 10～30min.Correlative incorporation time in high speed dispersion mixer is more than
10min is to enable correlative to be disperseed fully, it is ensured that the later stage processes the uniform of gained material
Property；Incorporation time is more than after 30min, and the dispersibility of material and homogeneity have been stablized, it is not necessary that continue
Power consumption.
As a kind of improvement of lithium ion battery anode material preparation method of the present invention, described step 4) high temperature
Cracking temperature is preferably 600-1100 DEG C.This is because temperature is less than 600 DEG C, organic polymer can not get fully
Carbonization, it will deteriorate the chemical property of material, such as efficiency step-down first；If but temperature is higher than 1100 DEG C,
Then can cause silicon monoxide generation dismutation reaction, change material intrinsic physical property and bring disadvantageous effect.
As a kind of improvement of lithium ion battery anode material preparation method of the present invention, described step 3) in first
Presoma and organic macromolecule mass ratio are 49:1～4:1.
As a kind of improvement of lithium ion battery anode material preparation method of the present invention, described organic polymer is
Colophonium or phenolic resin.
In order to realize foregoing invention purpose, present invention also offers a kind of lithium ion battery anode material, its bag
Include nanometer silicon monoxide, graphite and amorphous carbon coating layer；Described nanometer silicon monoxide granule embeds or parcel
In graphite, amorphous carbon coating layer is covered in the outer surface of graphite.
Nanometer silicon monoxide granule is embedded or is wrapped in graphite by lithium ion battery anode material of the present invention,
Avoid silicon monoxide granule to contact with the direct of electrolyte.Therefore, when there is electrochemical reaction, it is stone
Ink contacts formation SEI film, owing to the expansion rate of graphite itself is little, at the SEI that its surface is formed with electrolyte
Film can keep stability in cyclic process subsequently, thus effectively suppresses all untoward reaction；And at stone
Silicon monoxide within Mo is in close contact with graphite, and therefore electric conductivity accesses guarantee, so that electrochemical
Reaction is smoothed out.Further, since silicon monoxide and graphite recombination process can destroy original graphite unavoidably
The surface of grain and increase its surface activity point, so that needing to consume more in electrochemical reaction process subsequently
Lithium ion form SEI film, or have the very small amount silicon monoxide granule may be exposed at graphite surface,
Therefore the present invention is at one layer of soft carbon of graphite outer cladding, in order to modifies graphite surface, reduces its active site,
Improve efficiency first, and while avoiding exposed silicon monoxide directly to contact with electrolyte, add one
Layer conductive carbon layer and reduce its polarization.Therefore, compared with prior art, lithium ion battery of the present invention is used
Battery prepared by anode material, has the advantages such as cycle performance is excellent, battery core expansion is little, is highly suitable for disappearing
Take electronic product.
As a kind of improvement of lithium ion battery anode material of the present invention, described nanometer silicon monoxide is at anode material
Mass ratio in material is preferably 5-40%.If this is because its quality is less than 5%, prepared anode material
Capacity Ratio graphite improves limited, if but incorporation is higher than 40%, then cannot ensure the oxidation of all of nanometer one
Silicon grain can embed or be wrapped in graphite, once has unnecessary nanometer silicon monoxide to be exposed to outside graphite,
The chemical property of anode material will be caused to deteriorate because directly contacting with electrolyte.
As a kind of improvement of lithium ion battery anode material of the present invention, described graphite behaviour pelletizing type graphite or
Natural Sheet Graphite, it is also possible to be the mixing of the two；Nanometer silicon monoxide granule embeds and is scattered in people's pelletizing
In the internal voids of type graphite granule, or it is wrapped in the natural Sheet Graphite after nodularization.This is because people
Making spherical graphite and be usually second particle, the contained voidage inside it is higher, and void space is enough
Greatly, it is possible to effectively accommodate silicon monoxide granule；And natural Sheet Graphite can occur in mechanofusion process
Curling nodularization, by silicon monoxide particle encapsulation in wherein.
As a kind of improvement of lithium ion battery anode material of the present invention, the porosity of described artificial ball-type graphite
Being preferably greater than 30%, the lamella of natural Sheet Graphite is preferably sized to 50～500 μm.Artificial spherical graphite
Porosity is more than 30%, on the one hand guarantee to provide sufficient space to accommodate the silicon monoxide granule of embedding,
On the other hand may be provided for silicon monoxide space needed for the brought volumetric expansion of removal lithium embedded process, effectively
Ensure the integrity of whole silicon monoxide/graphite composite material granule, maintain stablizing of graphite outer surface SEI film
Property, improve the electrochemistry cycle performance of battery.The lamella of natural Sheet Graphite optimization is to protect more than 50 μm
Card Sheet Graphite occurs in mechanical fusion crimp time, it is possible to well by nanometer silicon monoxide particle encapsulation in
Wherein, the least Sheet Graphite is likely to result in outside a part of silicon monoxide granule is exposed to；If Sheet Graphite
Size more than 500 μm, although its can wrap up more silicon monoxide granule and stay enough holes come
Alleviating the volumetric expansion of silicon monoxide, but the granule after curling nodularization can be very big, this is unfavorable for battery electricity
, there is pole piece demoulding, or granule salient point exactly as modal in the making of pole pole piece, thus cold in the later stage
Cause pole piece disrumpent feelings during pressure or pierce through isolating membrane causing battery short circuit, there is potential safety hazard.
As a kind of improvement of lithium ion battery anode material of the present invention, the grain of described nanometer silicon monoxide granule
Footpath is preferably 20-500nm.Silicon monoxide particle diameter is in order to avoid granule is the least in mechanical fusion more than 20nm
During due to dispersion uneven and reunite, and the granule preparation difficulty that granule is less than 20nm, virtually
Also the cost of raw material will be increased.Silicon monoxide particle diameter is interior less than what 500nm allowed in Spherical graphite particles
Portion's pore size is limited, and excessive silicon monoxide granule would become hard to be embedded；For flake graphite also it is
The same reason, the excessive silicon monoxide granule of granule cannot be fully wrapped around by flake graphite.
As a kind of improvement of lithium ion battery anode material of the present invention, the thickness of described amorphous carbon coating layer
It is preferably 20-200nm.More than 20nm, amorphous carbon coating layer is to ensure that soft carbon-coating can be modified completely
Fortunately the graphite surface destroyed in fusion process, and can also be well by exposed for fraction one
Silicon oxide particle covers, thus effectively stops it to contact with the direct of electrolyte.Amorphous carbon coating layer is less than
Although 200nm is because amorphous carbon layer and thickens two aspects that can be further ensured that covering is above-mentioned, but
The increase of carbon coating layer content but can cause the loss of capacity；It addition, to be coated with blocked up carbon coating layer,
Then needing more organic polymer as carbon matrix precursor, this does in the later stage and is easy to occur when the heat of carbonization processes
Particle agglomeration, yield to product or the making to battery and chemical property all can bring negative shadow
Ring.
Accompanying drawing explanation
Below in conjunction with the accompanying drawings and detailed description of the invention, to lithium ion battery anode material of the present invention, preparation method
And beneficial effect is described in detail.
Fig. 1 behaves and makes the cross section SEM figure of spherical graphite.
Fig. 2 is the cross section SEM figure of the presoma first that the embodiment of the present invention 1 prepares.
Fig. 3 is the cross section SEM figure of the anode material that the embodiment of the present invention 1 prepares.
Fig. 4 is the surface SEM figure of natural Sheet Graphite.
Fig. 5 is the cross section SEM figure of the presoma first that the embodiment of the present invention 2 prepares.
Fig. 6 is micron order silicon monoxide and artificial spherical graphite mixed SEM figure in comparative example 1.
Fig. 7 is micron order silicon monoxide and natural Sheet Graphite mixed SEM figure in comparative example 2.
Detailed description of the invention
In order to make the goal of the invention of the present invention, technical scheme and Advantageous Effects become apparent from, below in conjunction with
The present invention is further elaborated by embodiment.It should be appreciated that the enforcement described in this specification
Example is only used to explain the present invention, is not intended to limit the present invention, and the formula of embodiment, ratio etc. can be because of
Ground suiting measures to different conditions makes a choice and result be there is no substantial effect.
Embodiment 1
It is that the artificial spherical graphite of 45% is by matter by silicon monoxide granule and porosity that mean diameter is 500nm
Measure and mix than 40:60, jointly put in high speed dispersion mixer, take out after 30min mixes；Then will
Mixture proceeds to grind in mechanical fusion machine, and grinding frequency is 2000r/min, and milling time is 20min, system
Obtain presoma first.The cross section SEM figure of artificial spherical graphite is as it is shown in figure 1, the presoma first for preparing
Cross section SEM schemes as shown in Figure 2, it is seen that, the nanometer silicon monoxide granule in this presoma has been inserted into and disperses
In the hole within spherical artificial graphite.
Afterwards, will presoma and Colophonium mixing first, wherein asphalt quality account for 10% (refer to Colophonium account for presoma and
The 10% of asphalt quality sum, following example are same), then by above-mentioned steps by high speed dispersion mixer and machinery
Syncretizing mechanism obtains secondary presoma.
Finally, obtained secondary presoma is transferred in high-temperature rotary furnace, protects at argon or nitrogen
Under, through 800 DEG C of high-temperature calcination carbonizations, obtain the silicon monoxide/graphite composite anode materials of the present invention.Sun
The cross section SEM of pole material schemes as it is shown on figure 3, wherein the thickness of carbon coating layer is about 200nm.
Embodiment 2
The silicon monoxide granule that mean diameter is 500nm is mixed with natural Sheet Graphite 40:60 in mass ratio,
The average platelet size of the natural Sheet Graphite used is about 100 μm, and its surface SEM schemes as shown in Figure 4；
Both are put into jointly in high speed dispersion mixer, take out after 30min mixes；Then mixture is turned
Entering in mechanical fusion machine and grind, grinding frequency is 6000r/min, and milling time is 10min, before preparing first
Drive body.The cross section SEM of the presoma first prepared schemes as shown in Figure 5, it is seen that, natural in this presoma
Sheet Graphite there occurs nodularization, and nanometer silicon monoxide granule is just wrapped in the native graphite of nodularization
In.
Afterwards, will presoma and Colophonium mix first, wherein asphalt quality accounts for 10%, then leads to by above-mentioned steps
Cross high speed dispersing mixer and mechanical fusion machine-processed secondary presoma.
Finally, obtained secondary presoma is transferred in high-temperature rotary furnace, protects at argon or nitrogen
Under, through 800 DEG C of high-temperature calcination carbonizations, obtain the silicon monoxide/graphite composite anode materials of the present invention.Sun
The cross section SEM figure of pole material is almost identical with the SEM figure of embodiment 1, and wherein the thickness of carbon coating layer is about
For 200nm.
Embodiment 3
The present embodiment is essentially identical with the step of embodiment 1, differs only in: the present embodiment used one
Silicon oxide is 5:95 with the mass ratio of artificial spherical graphite, and the porosity of artificial spherical graphite is 30%；Use
Organic high molecular polymer be phenolic resin, its quality accounts for (a presoma+phenolic resin) 3%, cracking
Carburizing temperature is 950 DEG C, carbon coating layer about 20nm after calcining cracking.Therefore, concrete scheme repeats no more.
Embodiment 4
The present embodiment is essentially identical with the step of embodiment 2, differs only in: the present embodiment used one
The mass ratio of silicon oxide and natural Sheet Graphite is 5:95, natural Sheet Graphite average platelet size be about
50μm；The organic high molecular polymer used is phenolic resin, and its quality accounts for (a presoma+phenolic resin)
3%, cracking carburizing temperature is 950 DEG C, carbon coating layer about 20nm after calcining cracking.Therefore, concrete scheme
Repeat no more.
Embodiment 5
The present embodiment is essentially identical with the step of embodiment 1, differs only in: the present embodiment used one
Silicon oxide is 20:80 with the mass ratio of artificial ball-type graphite, the wherein mean diameter of silicon monoxide about 20nm,
Artificial ball-type graphite porosity about 40%, the organic high molecular polymer of use is phenolic resin, and its quality accounts for
(a presoma+phenolic resin) 6%, cracking carburizing temperature is 950 DEG C, carbon coating layer after calcining cracking
About 120nm.Therefore, concrete scheme repeats no more.
Embodiment 6
The present embodiment is essentially identical with the step of embodiment 2, differs only in: the present embodiment used one
Silicon oxide is 20:80 with the mass ratio of natural Sheet Graphite, the wherein mean diameter of silicon monoxide about 20nm,
The average platelet size of natural Sheet Graphite is about 80 μm, and the organic high molecular polymer of use is phenolic aldehyde tree
Fat, its quality accounts for (a presoma+phenolic resin) 6%, and cracking carburizing temperature is 950 DEG C, splits through calcining
Carbon coating layer about 120nm after solution.Therefore, concrete scheme repeats no more.
Embodiment 7
The present embodiment is identical with the step of embodiment 1, differs only in: graphite is ball-type Delanium and sky
So mixing of Sheet Graphite, its mass ratio is 1:1.Therefore, concrete scheme repeats no more.
Comparative example 1
By the micron-sized silicon monoxide (D50 about 5 microns) commonly used at present and artificial spherical graphite (hole
Rate is 45%) mechanical mixture of 40:60 in mass ratio, as anode of lithium ion battery active material.This anode material
The SEM of material schemes as shown in Figure 6.
Comparative example 2
By the micron-sized silicon monoxide (D50 about 5 microns) commonly used at present and natural Sheet Graphite (lamella
Size about 100 microns) mechanical mixture of 40:60 in mass ratio, as anode of lithium ion battery active material.Should
The SEM of anode material schemes as shown in Figure 7.
Comparative example 3
The present embodiment is essentially identical with the step of embodiment 1, differs only in: this comparative example used one
Silicon oxide is 50:50 with the mass ratio of spherical graphite, and the porosity of artificial spherical graphite is 30%；Use has
Machine high molecular polymer is phenolic resin, and cracking carburizing temperature is 950 DEG C.Therefore, concrete scheme repeats no more.
Comparative example 4
The present embodiment is essentially identical with the step of embodiment 2, differs only in: this comparative example used one
The mass ratio of silicon oxide and natural Sheet Graphite is 50:50, natural Sheet Graphite average platelet size be about
80μm；The organic high molecular polymer used is phenolic resin, and cracking carburizing temperature is 950 DEG C.Therefore,
Concrete scheme repeats no more.
Comparative example 5
The present embodiment is essentially identical with the step of embodiment 1, differs only in: the side that this comparative example is used
Method be the preparation of high energy spheroidal graphite method first with secondary presoma, the mass ratio of silicon monoxide and spherical graphite is 40:60,
The porosity of artificial spherical graphite is 30%；The organic high molecular polymer used is phenolic resin, cracks carbon
Changing temperature is 950 DEG C.Therefore, concrete scheme repeats no more.
Comparative example 6
Chemical surfactant (such as cetyl trimethylammonium bromide) is used to disperse 500 nanometer silicon monoxides,
And by being that 40:60 mixes with the mass ratio of spherical graphite, the porosity of the most artificial ball-type graphite is 30%,
Ultrasonic agitation 60min in dehydrated alcohol, is then drying prepared presoma first.Carbon coated flow process subsequently with
Embodiment 1 is identical, repeats no more.
The assembling of lithium ion battery
Respectively with 1～6 lithium ion battery anode materials prepared in embodiment 1～7 and comparative example for anode activity
Material, adds in solvent according to a certain percentage by itself and binding agent, thickening agent, conductive agent, agitated preparation
After form slurry, according to coating, cold pressing and the operation such as cut-parts prepares anode strip；Subsequently with corresponding cathode sheets
Lithium ion battery is prepared, by embodiment 1～7 anode material through operations such as winding, fluid injection and chemical conversions with isolating membrane
Numbered K1～K7 of lithium ion battery that material prepares, the lithium ion battery that comparative example 1～6 anode material prepares is compiled
Number it is D1～D6.
Battery performance test
Use following procedure that above-mentioned 10 groups of lithium ion batteries are tested: every Battery pack all takes 5, often
With 1C constant-current charge to 4.3V under temperature, after constant voltage to 0.05C, put with 1C constant current again after standing half an hour
Electricity is to 3.0V, then stands half an hour, circulates 500 times with this program.
After first time discharge and recharge, calculate its capacity calculating correspondence first after efficiency, and loop test keep
Rate, wherein, charging capacity * 100% of the discharge capacity of efficiency=for the first time/for the first time first, the capacity in N week is protected
Discharge capacity * 100% of discharge capacity/the first week in holdup=the N week.Experimental result is as shown in table 1.
Table 1, embodiment 1～7 and the battery performance test result of comparative example 1～6
As can be seen from Table 1:
1) by the contrast of K1, K2 and D1, D2 it can be seen that use the silicon monoxide/graphite of the present invention
The battery that composite anode materials is made, efficiency and capability retention aoxidize far above the most existing one first for they
The battery that silicon and graphite mix and prepares.This is due to the oxidation in lithium ion battery anode material of the present invention
Silicon is coated in graphite, does not directly contact with electrolyte, and the consumption lithium ion that will not react is to form SEI
Film, therefore its first efficiency be greatly enhanced.Meanwhile, in cyclic process subsequently, silicon monoxide
Expand and be only inside graphite, integrity can be kept for whole granule, also would not cause
The destruction of graphite surface SEI film, the consumption to electrolyte is substantially reduced, it is ensured that circulation can persistently be carried out,
And have higher capability retention；
2) strengthening the content of silicon monoxide, such as D3 and D4 group, its charging capacity increases, but relative head
Secondary efficiency is but substantially reduced, and this is due to such substantial amounts of silicon monoxide, it is impossible to have fully embedded between ball-type graphite
Being coated with in gap or by Sheet Graphite, left over a part of nanometer silicon monoxide on surface, this part causes ratio
Surface area increases, and direct and electrolyte contacts, after discharge and recharge in first week, needs to consume substantial amounts of lithium
Form SEI film.Along with the carrying out of circulation, the expansion of this partial particulate does not has cushion space, but is broken
Continue and electrolyte contacts after Huai, consume limited electrolyte again and again, thus cause battery core quickly to be jumped
Water.Therefore the preparation of such material, wherein silicon monoxide content limited no more than this explanation 40%.
3) such negative material of preparing of high energy ball mill is used, such as D5 group, because of its gesture during spheroidal graphite
The broken of graphite granule must be caused, thus be not provided that sufficient space accommodates nanometer silicon monoxide and embeds, cause
Significant portion of silicon monoxide granule is exposed to, outside graphite granule, directly contact with electrolyte, causes first effect
Being greatly lowered, cycle performance deteriorates.
4) chemical organic solvent dispersion silicon nanoparticle is used, it is intended to be inserted into the side in graphite granule gap
Method, because not forcing external force, overwhelming majority nanometer silicon monoxide granule is only attached to graphite granule surface,
And in non-entry graphite gaps, first effect certainly will be caused to reduce, electrolyte consumes too fast, and cycle performance deteriorates.
Furthermore, it is necessary to explanation, the present invention uses silicon monoxide and the graphite compound preparation sun of different content
Pole material, its chemical property still ratio is by silicon monoxide and the mixed electrochemistry of graphite standard machinery
Can be excellent, do not repeating at this.
The announcement of book and teaching according to the above description, those skilled in the art in the invention can also be to above-mentioned
Embodiment carries out suitable change and amendment.Therefore, the invention is not limited in disclosed and described above
Some modifications and changes of the present invention be should also be as falling into the guarantor of the claim of the present invention by detailed description of the invention
In the range of protecting.Although additionally, employ some specific terms in this specification, but these terms are simply
Facilitate explanation, the present invention is not constituted any restriction.
Claims (10)
1. a lithium ion battery anode material, it is characterised in that: include nanometer silicon monoxide, graphite and nothing
Setting carbon coating layer；Described nanometer silicon monoxide granule embeds or is wrapped in graphite, amorphous carbon coating layer
It is covered in the outer surface of graphite.
Lithium ion battery anode material the most according to claim 1, it is characterised in that: described nanometer one
Silicon oxide mass ratio in anode material is 5-40%.
Lithium ion battery anode material the most according to claim 1, it is characterised in that: described graphite is
Artificial ball-type graphite or natural Sheet Graphite, it is also possible to be the mixing of the two；Nanometer silicon monoxide granule embeds
And be scattered in the internal voids of artificial ball-type graphite granule, or it is wrapped in the natural Sheet Graphite after nodularization
In.
Lithium ion battery anode material the most according to claim 3, it is characterised in that: described people's pelletizing
The porosity of type graphite is more than 30%, and the lamella size of natural Sheet Graphite is 50～500 μm.
Lithium ion battery anode material the most according to claim 1, it is characterised in that: described nanometer one
The particle diameter of silicon oxide particle is 20-500nm.
Lithium ion battery anode material the most according to claim 1, it is characterised in that: described amorphous
The thickness of carbon coating layer is 20-200nm.
7. a lithium ion battery anode material preparation method, it is characterised in that comprise the following steps:
1) nanometer silicon monoxide and graphite are positioned over mix homogeneously in high speed dispersion mixer；
2) by 1) mixture prepared is transferred in mechanical fusion machine merge and grinds, and grinding frequency is
2000～6000r/min, milling time is 10～60min, obtain graphite parcel nanometer silicon monoxide first before
Drive body；
3) will mix homogeneously during presoma and organic polymer are positioned over high speed dispersion mixer first, the most again
Proceed in mechanical fusion machine, under 2000～6000r/min frequencies, grind 10～60min, obtain secondary presoma；
4) secondary presoma is placed in high-temperature rotary furnace, under inert gas shielding, Pintsch process carbonization,
Obtain lithium ion battery anode material.
Lithium ion battery anode material preparation method the most according to claim 7, it is characterised in that: institute
State step 1) or 3) incorporation time be 10～30min.
Lithium ion battery anode material preparation method the most according to claim 7, it is characterised in that: institute
State step 4) Pintsch process temperature be 600-1100 DEG C.
Lithium ion battery anode material preparation method the most according to claim 7, it is characterised in that: institute
Stating organic polymer is Colophonium or phenolic resin, step 3) in presoma and organic macromolecule mass ratio first
For 49:1～4:1.
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