CN109888266A - A kind of silicon-based anode piece and preparation method thereof and lithium ion battery - Google Patents
A kind of silicon-based anode piece and preparation method thereof and lithium ion battery Download PDFInfo
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- CN109888266A CN109888266A CN201910151505.0A CN201910151505A CN109888266A CN 109888266 A CN109888266 A CN 109888266A CN 201910151505 A CN201910151505 A CN 201910151505A CN 109888266 A CN109888266 A CN 109888266A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of silicon-based anode piece and preparation method thereof and lithium ion batteries.The cathode coating of silicon-based anode piece provided by the invention includes the first coating on collector and the second coating in first coating, active material in the first coating includes silicon based anode material, active material in the second coating does not include silicon based anode material, and lithium is contained on the second coating surface.The preparation method includes 1) forming first coating on a current collector with the first slurry coating containing silicon based anode material；2) second coating is formed in first coating with the second slurry for not including silicon based anode material；3) lithium is mixed in advance to the pole piece progress containing second coating, obtains the silicon-based anode piece.Silicon-based anode piece provided by the invention avoids silica-base material during prelithiation of the pole piece containing silicon based anode material and contacts with the direct of lithium metal, has been obviously improved energy density and cyclical stability.
Description
Technical field
The invention belongs to energy storage technologies field, it is related to a kind of pole piece and its preparation method and application more particularly to one
Kind silicon-based anode piece and preparation method thereof and lithium ion battery.
Background technique
Since lithium ion battery has high voltage, high-energy density, high circulation service life, low self-discharge rate, light-weight and nothing
The advantages that memory effect, realizes in various fields and is widely applied.As electrical equipment is to capacity of lithium ion battery requirement
Continuous improvement, the expectation that people promote lithium ion battery energy density is higher and higher.Other than traditional digital product,
Also mass is lighter, volume is smaller, output voltage and power are close continually developing for energy storage device, electric tool, electric car etc.
Higher lithium ion battery is spent, the lithium ion battery for developing high-energy density is the important R&D direction of lithium battery industry.
In order to manufacture and design the lithium ion battery with higher energy density, it is necessary to use the positive and negative anodes material of higher gram volume
Material.Conventional graphite negative material theoretical capacity is 370mAh/g, it is difficult to support the lithium ion battery energy density water of 300Wh/kg
It is flat.Silicon based anode material reaches as high as 4200mAh/g (elemental silicon) as its capacity of the lithium ion battery negative material of a new generation.
Have been carried out the oxidation Asia silicon materials SiOx of Commercialization application and lithium ion battery energy that nickelic tertiary cathode material is arranged in pairs or groups
Metric density is applied to electric passenger vehicle, and practical cruising ability is greater than 500km.
However in actual use, there is the problems such as first effect is insufficient, and material circulation stability is poor in silicon based anode material.
Si simple substance completely fills situation lower volume inflatable 300% in lithium battery, the problems such as causing pole piece dusting, fall off, deposits in practical application
In larger difficulty.SiOx expansion is smaller, and stability is preferable, but its own can react with the active Li in battery, consumption
Li ion is to reduce the first effect and energy density of battery；Particle Breakage caused by volume change may not in cyclic process
For medium well at SEI film, persistently consuming Li ion causes capacity retention ratio to reduce.For the application problem for solving SiOx, pole can be used
Piece prelithiation technology --- appropriate metal lithium simple substance is added in battery pole piece preparation process, is being used to compensate silicon-based anode
The active lithium consumed in the process.This method is expected to obviously improve the energy density and stable circulation of silicon-based anode lithium ion battery
Property.
Lithium simple substance is used during general prelithiation, is directly contacted by distinct methods with cathode pole piece.Lithium simple substance and negative
Pole material directly reacts, and forms prelithiation material and pole piece.When negative electrode tab of the use containing silicon based anode material carries out pre- lithium
When change, it is easy to cause the uneven of material granule structure, so that the adverse consequences such as Particle Breakage occur；The uneven embedding lithium formed
Product stability is poor, and capacity reduces rapidly during following cycle, it is possible to create minus effect.
CN109004182A discloses a kind of method of lithium ion battery silicon substrate cathode pole piece prelithiation, specifically in inertia
In atmosphere, silicon-based anode pole piece is contacted with interface modifier；Then the silicon-based anode pole piece that will be handled again through interface modifier
It is contacted with lithium metal；It is dry；Remove the extra lithium metal of silicon-based anode pole piece；The interface modifier by organic solvent and
It is formed containing lithium electrolyte.The interface modifier of the program can be used as lithium ion transport medium, and material is facilitated to be that lithium metal connects
Uniform when touching, controllable lithiumation.But this method is limited to the uniformity promotion of lithium embedding in lithiated product.
CN105470465A discloses the prelithiation treatment process and device of a kind of silicon-based anode, and treatment process includes even
Slurry, coating, two step constant current pulsed deposition process electrodeposit metals lithiums, DMC impregnate, drying and etc..The prelithiation of the program
Process requirement carries out electro-deposition in special device, extremely cumbersome, can obviously increase production cost, is unfavorable for industry metaplasia
It produces.
CN105405679A discloses a kind of ternary oxide and hard carbon based super capacitor, the method for cathode pre-doping
Are as follows: the positive and negative plate prepared through lamination or is wound into battery core, is put into aluminum plastic film, aluminum hull or steel shell；It will be with lithium source
Third pole is packed into suitable position, convenient for cathode pre-doping.This method is a kind of improvement to electro-deposition pre-doping, although nothing
Special device is needed, but needs to be added third pole lithium source pole, and be powered to realize lithium doping, therefore in industry
Metaplasia is not very convenient on producing.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of silicon-based anode piece and preparation method thereof
And lithium ion battery.In silicon-based anode piece provided by the invention, the stability of silicon based anode material is good, and embedding lithium is uniform, and circulation is steady
It is qualitative good.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of silicon-based anode piece, the cathode coating of the silicon-based anode piece includes being located at collection
First coating on fluid and the second coating in first coating, the active material in the first coating include that silicon substrate is negative
Pole material, the active material in the second coating do not include silicon based anode material, and lithium is contained on the second coating surface.
Silicon-based anode piece provided by the invention includes two coating layer of active substance, the second coating without silicon based anode material
Lithium metal is completely cut off to contact with the direct of silicon based anode material in first coating, pre- lithium is avoided by the pole piece structure of this optimization
The direct haptoreaction of lithium metal and the silicon based anode material in pole piece during change, to improve prelithiation silicon-based anode pole
Tablet stability.There is the characteristics of high-energy density, high stability using the lithium ion battery that the pole piece designs.
Silicon-based anode piece provided by the invention solves after silica-base material is contacted with lithium by coating second coating because connecing
A series of problems, such as contact reaction is very fast and generates Particle Breakage, stability difference and poor circulation.
Silicon-based anode piece provided by the invention includes cathode coating and collector.
It is used as currently preferred technical solution below, but not as the limitation to technical solution provided by the invention, leads to
Following preferred technical solution is crossed, can preferably reach and realize technical purpose and beneficial effect of the invention.
As currently preferred technical solution, the silicon based anode material includes silicon and/or the sub- silicon of oxidation, preferably oxygen
Change sub- silicon.In the present invention, it can be silicon, or aoxidize sub- silicon, can also be silicon that the silicon and/or the sub- silicon of oxidation, which refer to,
With the combination for aoxidizing sub- silicon.
Preferably, the sub- chemistry of silicones formula of the oxidation is SiOx, wherein 0 < x < 1, such as x is 0.1,0.2,0.4,0.6,
0.8 or 0.9 etc..
Preferably, the active material in the first coating further includes containing carbon negative pole material.
Preferably, the carbon containing negative electrode active material in the first coating includes graphite and/or amorphous carbon material.
Preferably, the graphite includes artificial graphite and/or natural graphite.
Preferably, the amorphous carbon material includes soft carbon and/or hard carbon.
Preferably, silicon based anode material and the mass ratio containing carbon negative pole material are 3:97-100:0 in the first coating,
Such as 3:97,20:80,30:70,40:60,50:50,60:40,70:80,90:10 or 100:0 etc., it is not limited to listed
The numerical value of act, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, the active material in the second coating includes carbon containing negative electrode active material.
Preferably, the carbon containing negative electrode active material includes graphite and/or amorphous carbon material.
Preferably, the graphite includes artificial graphite and/or natural graphite.
Preferably, the amorphous carbon material includes soft carbon and/or hard carbon.
Preferably, the lithium that the second coating surface is contained is the compound of lithium simple substance and/or lithium, the compound of the lithium
The chemical valence of middle lithium is negative value.The lithium of lithium simple substance and negative valency has reproducibility, can preferably promote the performance of electrode.
Preferably, the compound of the lithium includes the carbide of lithium.I.e. elemental lithium is present in carbon material in the form of LixC
In the middle.
Preferably, the collector includes copper foil.
Preferably, the first coating with a thickness of 5-300 microns, such as 5 microns, 10 microns, 50 microns, 100 microns,
150 microns, 200 microns, 250 microns or 300 microns etc., it is not limited to cited numerical value, in the numberical range other
Unlisted numerical value is equally applicable.If the thickness of first coating is blocked up, it will lead to electrolyte and be difficult to infiltrate, the internal resistance of cell is big；
If the thickness of first coating is excessively thin, it is low to will lead to active material ratio, influences battery energy density.
Preferably, the second coating with a thickness of 1-100 microns, such as 1 micron, 10 microns, 20 microns, 40 microns,
60 microns, 80 microns or 100 microns etc., it is not limited to cited numerical value, other interior unlisted numbers of the numberical range
It is worth equally applicable.If the thickness of second coating is blocked up, also results in electrolyte and be difficult to infiltrate, the internal resistance of cell is big；If the
The thickness of two coatings is excessively thin, will lead to and is difficult to ensure first coating is completely covered, to lose the function of second coating itself.
Preferably, in the silicon-based anode piece, the mass fraction of elemental lithium is 0.05-10%, for example, 0.05%, 0.1%,
1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10% etc., it is not limited to cited numerical value, the numerical value model
Other unlisted numerical value are equally applicable in enclosing.If the mass fraction of lithium is excessive, active lithium excess will lead to, in cost of idleness
While reduce battery energy density；If the mass fraction of lithium is too small, the amount that will lead to addition active lithium is insufficient, Wu Fada
The purpose of battery energy density and cyclical stability is improved to prelithiation pole piece.Elemental lithium described here refers to second coating surface
Lithium.
Preferably, first coating one side coating or double spread on a current collector.
As currently preferred technical solution, the first coating includes active material, conductive agent and binder.
Preferably, the conductive agent includes any one in graphite powder, active carbon, carbon black or acetylene black or at least two
Combination.
Preferably, the binder includes polytetrafluoroethylene (PTFE), Kynoar, hydroxypropyl methyl cellulose, carboxymethyl fibre
Tie up in plain sodium or butadiene-styrene rubber any one or at least two combination.
Preferably, in the first coating, the mass fraction of active material is 60-98.9%, for example, 60%, 70%,
80%, 90% or 98.9% etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are same
It is applicable in；The mass fraction of conductive agent be 0.1-30%, such as 0.1%, 0.5%, 1%, 5%, 10%, 15%, 20%, 25% or
30% etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable；Binder
Mass fraction is 1-30%, such as 1%, 5%, 10%, 15%, 20%, 25% or 30% etc., it is not limited to cited
Numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
As currently preferred technical solution, the second coating includes active material, conductive agent and binder.
Preferably, the conductive agent includes any one in graphite powder, active carbon, carbon black or acetylene black or at least two
Combination.
Preferably, the binder includes polytetrafluoroethylene (PTFE), Kynoar, hydroxypropyl methyl cellulose, carboxymethyl fibre
Tie up in plain sodium or butadiene-styrene rubber any one or at least two combination.
Preferably, in the second coating, the mass fraction of active material is 60-98.9%, for example, 60%, 70%,
80%, 90% or 98.9% etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are same
It is applicable in；The mass fraction of conductive agent be 0.1-30%, such as 0.1%, 0.5%, 1%, 5%, 10%, 15%, 20%, 25% or
30% etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable；Binder
Mass fraction is 1-30%, such as 1%, 5%, 10%, 15%, 20%, 25% or 30% etc., it is not limited to cited
Numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Second aspect, the present invention provide a kind of preparation method of silicon-based anode piece as described in relation to the first aspect, the method packet
Include following steps:
(1) first coating is formed on a current collector with the first slurry coating containing silicon based anode material, obtain containing first
The pole piece of coating；
(2) shape in the first coating of step (1) pole piece is coated on the second slurry for not including silicon based anode material
At second coating, the pole piece containing second coating is obtained；
(3) lithium is mixed in advance in step (2) the pole piece progress containing second coating, obtains the silicon-based anode piece.
Preparation method provided by the invention forms second coating by the second slurry of coating, avoids containing silicon based anode material
Pole piece during prelithiation silica-base material and lithium metal directly contact, and thus bring silica-base material denaturation, no
Uniform embedding lithium, broken even pulverizing problem.Preparation method provided by the invention is easy to operate, and process is short, is adapted for industrialization
Large-scale production.
As currently preferred technical solution, the preparation method of step (1) first slurry includes: by formula ratio
Active material, conductive agent and binder are mixed with solvent, obtain first slurry.
Preferably, the solvent includes water；
Preferably, in first slurry, the mass fraction of active material is 20-80%, for example, 20%, 30%, 40%,
50%, 60%, 70% or 80% etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range
It is equally applicable.
Preferably, in step (1), the method for forming first coating includes: that the first slurry is sprayed on collector
And it is dried；
Or slurry is coated on collector and is dried using transfer coater.
Preferably, the preparation method of step (2) second slurry include: by the active material of formula ratio, conductive agent and
Binder is mixed with solvent, obtains second slurry.
Preferably, the solvent includes water.
Preferably, in second slurry, the mass fraction of active material is 20%-80%, for example, 20%, 30%,
40%, 50%, 60%, 70% or 80% etc., it is not limited to cited numerical value, other are unlisted in the numberical range
Numerical value is equally applicable.
Preferably, in step (2), the method for forming second coating includes: that second coating is sprayed on first coating
It goes up and is dried；
Or slurry is coated on collector and is dried using transfer coater.
As currently preferred technical solution, in step (3), further includes: before mixing lithium in advance, to described in step (2)
Pole piece containing second coating carries out roll-in.
Preferably, the pressure of the roll-in is 10-200 tons, such as 10 tons, 20 tons, 50 tons, 75 tons or 100 tons etc., but simultaneously
It is not limited only to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
As currently preferred technical solution, step (3) the pre- method for mixing lithium includes: using lithium powder, in step
(2) pole piece containing second coating carries out trembling powder.
Alternatively, the pole piece containing second coating described in step (2) is rolled using lithium band.
As the further preferred technical solution of preparation method of the present invention, the described method comprises the following steps:
(1) it mixes, obtains with solvent by the silicon based anode material of formula ratio, containing carbon negative pole material, conductive agent and binder
First slurry on a current collector by first slurry coating obtains the pole piece containing first coating after dry；
Wherein, in first slurry, silicon based anode material and the total mass fraction containing carbon negative pole material are 20-80%；
(2) active material not comprising silicon based anode material, conductive agent and the binder of formula ratio are mixed with solvent, is obtained
To the second slurry, the second slurry is coated in the first coating of step (1) pole piece, is obtained after dry containing second coating
Pole piece；
Wherein, in second slurry, the mass fraction of active material is 20-80%；
(3) roll-in is carried out with 10-200 tons of pressure to the pole piece containing second coating described in step (2), and is mixed in advance
Lithium obtains the silicon-based anode piece；
Wherein, the pre- method for mixing lithium include using lithium powder the pole piece containing second coating tremble powder or
Person is rolled using lithium band in the pole piece containing second coating.
The third aspect, the present invention provide a kind of lithium ion battery, and the lithium ion battery includes as described in relation to the first aspect
Silicon-based anode piece.
Lithium ion battery provided by the invention has high-energy density and high circulation stability.
Lithium ion battery provided by the invention can be by by silicon-based anode piece provided by the invention and the anode that separately prepares
Pole piece, isolation film are wound and enter the operation such as shell, fluid injection, encapsulation and obtain.
Compared with prior art, the invention has the following advantages:
(1) silicon-based anode piece provided by the invention avoids silicon substrate during prelithiation of the pole piece containing silicon based anode material
Material is directly contacted with lithium metal, is conducive to maintain stability of the silicon based anode material in pole piece, solves silica-base material
The denaturation of bring silica-base material, uneven embedding lithium, broken even pulverizing problem are directly contacted with lithium, have been obviously improved energy density
And cyclical stability.The energy density of silicon-based anode piece provided by the invention is up to 280Wh/kg, and cycle efficieny is reachable for the first time
89%, 0.5C/1C carries out 400 circulation volume conservation rates and carries out 400 circulations appearances up to C/1C at 94%, 45 DEG C at 25 DEG C
Conservation rate is measured up to 92%.
(2) preparation method provided by the invention forms second coating by the second slurry of coating, avoids containing silicon-based anode
The pole piece of material silica-base material during prelithiation is contacted with the direct of lithium metal, and preparation method provided by the invention is grasped
Make simply, process is short, is adapted for industrialization large-scale production.
Specific embodiment
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, below further specifically to the present invention
It is bright.But following embodiments is only simple example of the invention, does not represent or limit the scope of the present invention, this
Invention protection scope is subject to claims.
The following are typical but non-limiting embodiments of the invention:
Embodiment 1
The present embodiment provides a kind of silicon-based anode piece, the cathode coating of the silicon-based anode piece includes being coated on copper foil afflux
First coating on body and the second coating being coated in first coating.
The first coating includes active material, conductive agent and binder, and wherein active material is to aoxidize sub- silicon SiO0.9,
Conductive agent is graphite powder, and binder is sodium carboxymethylcellulose.In the first coating, the mass fraction of active material is
80%, the mass fraction of conductive agent is 5%, and the mass fraction of binder is 15%.
The second coating includes active material, conductive agent and binder, and wherein active material is natural graphite, conductive agent
For graphite powder, binder is sodium carboxymethylcellulose.In the second coating, the mass fraction of active material is 94%, conductive
The mass fraction of agent is 2%, and the mass fraction of binder is 3%.The second coating surface also carbon containing lithium simple substance and lithium
Compound, in silicon-based anode piece provided in this embodiment, the mass fraction of elemental lithium is 1%.
In the silicon-based anode piece, first coating with a thickness of 60 microns, second coating with a thickness of 30 microns, first applies
Layer double spread in copper foil current collector.
Silicon-based anode piece provided in this embodiment is prepared as follows:
(1) silicon based anode material of formula ratio (is aoxidized into sub- silicon SiO0.9), conductive agent and binder mixed with water, obtain
First slurry is coated in copper foil current collector by the first slurry, obtains the pole piece containing first coating after dry；
Wherein, in first slurry, the mass fraction of silicon based anode material is 45%；
(2) active material not comprising silicon based anode material, conductive agent and the binder of formula ratio are mixed with water, is obtained
Second slurry is coated in the first coating of step (1) pole piece by the second slurry, is obtained after dry containing second coating
Pole piece；
Wherein, in second slurry, the mass fraction of active material is 50%；
(3) lithium powder is used to tremble powder to be mixed lithium in advance the pole piece containing second coating described in step (2), and with 20 tons
Pressure carries out roll-in, and, obtain the silicon-based anode piece.
The performance test results of silicon based anode material provided in this embodiment are shown in Table 1.
Embodiment 2
The present embodiment provides a kind of silicon-based anode piece, the cathode coating of the silicon-based anode piece includes being coated on copper foil afflux
First coating on body and the second coating being coated in first coating.
The first coating includes active material, conductive agent and binder, and wherein active material is to aoxidize sub- silicon SiO0.5With
Artificial graphite (mass ratio 25:75), conductive agent are carbon black, and binder is Kynoar.In the first coating, active material
Mass fraction be 88%, the mass fraction of conductive agent is 4%, and the mass fraction of binder is 8%.
The second coating includes active material, conductive agent and binder, and wherein active material is artificial graphite, conductive agent
For carbon black, binder is Kynoar.In the second coating, the mass fraction of active material is 96.5%, conductive agent
Mass fraction is 1%, and the mass fraction of binder is 2.5%.The second coating surface also carbonization containing lithium simple substance and lithium
Object, in silicon-based anode piece provided in this embodiment, the mass fraction of elemental lithium is 0.5%.
In the silicon-based anode piece, first coating with a thickness of 90 microns, second coating with a thickness of 20 microns, first applies
Layer double spread in copper foil current collector.
Silicon-based anode piece provided in this embodiment is prepared as follows:
(1) negative electrode active material of formula ratio (aoxidizing sub- silicon and artificial graphite), conductive agent and binder are mixed with water,
The first slurry is obtained, first slurry is coated in copper foil current collector, obtains the pole piece containing first coating after dry；
Wherein, in first slurry, the mass fraction of negative electrode active material is 80%；
(2) active material not comprising silicon based anode material, conductive agent and the binder of formula ratio are mixed with water, is obtained
Second slurry is coated in the first coating of step (1) pole piece by the second slurry, is obtained after dry containing second coating
Pole piece；
Wherein, in second slurry, the mass fraction of active material is 80%；
(3) lithium powder is used tremble powder the pole piece containing second coating described in step (2) to be mixed lithium in advance, and with
200 tons of pressure carries out roll-in, and obtains the silicon-based anode piece.
The performance test results of silicon based anode material provided in this embodiment are shown in Table 1.
Embodiment 3
The present embodiment provides a kind of silicon-based anode piece, the cathode coating of the silicon-based anode piece includes being coated on copper foil afflux
First coating on body and the second coating being coated in first coating.
The first coating includes active material, conductive agent and binder, and wherein active material is to aoxidize sub- silicon SiO0.2With
Artificial graphite (mass ratio 13:87), conductive agent are acetylene black, and binder is butadiene-styrene rubber.In the first coating, active material
Mass fraction be 92%, the mass fraction of conductive agent is 2%, and the mass fraction of binder is 6%.
The second coating includes active material, conductive agent and binder, and wherein active material is that amorphous carbon material is (hard
Carbon), conductive agent is acetylene black, and binder is sodium carboxymethylcellulose.In the second coating, the mass fraction of active material is
93%, the mass fraction of conductive agent is 2%, and the mass fraction of binder is 4.7%.Also contain lithium list in the second coating surface
The carbide of matter and lithium, in silicon-based anode piece provided in this embodiment, the mass fraction of elemental lithium is 0.3%.
In the silicon-based anode piece, first coating with a thickness of 100 microns, second coating with a thickness of 10 microns, first
Coating double spread in copper foil current collector.
Silicon-based anode piece provided in this embodiment is prepared as follows:
(1) by the negative electrode active material of formula ratio (including aoxidizing sub- silicon and artificial graphite), conductive agent and binder and water
Mixing, obtains the first slurry, first slurry is coated in copper foil current collector, obtains the pole containing first coating after dry
Piece；
Wherein, in first slurry, the mass fraction of negative electrode active material is 20%；
(2) active material not comprising silicon based anode material, conductive agent and the binder of formula ratio are mixed with water, is obtained
Second slurry is coated in the first coating of step (1) pole piece by the second slurry, is obtained after dry containing second coating
Pole piece；
Wherein, in second slurry, the mass fraction of active material is 20%；
(3) roll-in is carried out with 10 tons of pressure to the pole piece containing second coating described in step (2), and is being contained using lithium band
There is the pole piece of second coating to be rolled to carry out mixing lithium in advance, obtains the silicon-based anode piece.
The performance test results of silicon based anode material provided in this embodiment are shown in Table 1.
Embodiment 4
The present embodiment provides a kind of silicon-based anode piece, the cathode coating of the silicon-based anode piece includes being coated on copper foil afflux
First coating on body and the second coating being coated in first coating.
The first coating includes active material, conductive agent and binder, wherein active material be silicon and artificial graphite (3:
97), conductive agent is acetylene black, and binder is hydroxypropyl methyl cellulose.In the first coating, the mass fraction of active material
It is 95%, the mass fraction of conductive agent is 1%, and the mass fraction of binder is 4%.
The second coating includes active material, conductive agent and binder, and wherein active material is that amorphous carbon material is (soft
Carbon), conductive agent is acetylene black, and binder is butadiene-styrene rubber.In the second coating, the mass fraction of active material is 93%,
The mass fraction of conductive agent is 3%, and the mass fraction of binder is 3.8%.The second coating surface also contain lithium simple substance with
The carbide of lithium, in silicon-based anode piece provided in this embodiment, the mass fraction of elemental lithium is 0.2%.
In the silicon-based anode piece, first coating with a thickness of 110 microns, second coating with a thickness of 30 microns, first
Coating double spread in copper foil current collector.
The preparation method of silicon-based anode piece provided in this embodiment is referring to embodiment 1.
The performance test results of silicon based anode material provided in this embodiment are shown in Table 1.
Embodiment 5
The present embodiment provides a kind of silicon-based anode piece, the cathode coating of the silicon-based anode piece includes being coated on copper foil afflux
First coating on body and the second coating being coated in first coating.
The first coating includes active material, conductive agent and binder, and wherein active material is to aoxidize sub- silicon SiO0.8,
Conductive agent is graphite powder, and binder is sodium carboxymethylcellulose.In the first coating, the mass fraction of active material is
98.9%, the mass fraction of conductive agent is 0.1%, and the mass fraction of binder is 1%.
The second coating includes active material, conductive agent and binder, and wherein active material is artificial graphite, conductive agent
For graphite powder, binder is sodium carboxymethylcellulose.In the second coating, the mass fraction of active material is 98.9%, is led
The mass fraction of electric agent is 0.1%, and the mass fraction of binder is 1%.Also contain lithium simple substance and lithium in the second coating surface
Carbide, in silicon-based anode piece provided in this embodiment, the mass fraction of elemental lithium is 10%.
In the silicon-based anode piece, first coating with a thickness of 5 microns, second coating with a thickness of 1 micron, first coating
The double spread in copper foil current collector.
The preparation method of silicon-based anode piece provided in this embodiment is referring to embodiment 1.
The performance test results of silicon based anode material provided in this embodiment are shown in Table 1.
Embodiment 6
The present embodiment provides a kind of silicon-based anode piece, the cathode coating of the silicon-based anode piece includes being coated on copper foil afflux
First coating on body and the second coating being coated in first coating.
The first coating includes active material, conductive agent and binder, and wherein active material is to aoxidize sub- silicon SiO0.7,
Conductive agent is graphite powder, and binder is sodium carboxymethylcellulose.In the first coating, the mass fraction of active material is
60%, the mass fraction of conductive agent is 30%, and the mass fraction of binder is 10%.
The second coating includes active material, conductive agent and binder, and wherein active material is natural graphite, conductive agent
For graphite powder, binder is sodium carboxymethylcellulose.In the second coating, the mass fraction of active material is 60%, conductive
The mass fraction of agent is 10%, and the mass fraction of binder is 30%.The second coating surface is also containing lithium simple substance and lithium
Carbide, in silicon-based anode piece provided in this embodiment, the mass fraction of elemental lithium is 0.05%.
In the silicon-based anode piece, first coating with a thickness of 200 microns, second coating with a thickness of 100 microns, first
Coating double spread in copper foil current collector.
The preparation method of silicon-based anode piece provided in this embodiment is referring to embodiment 1.
The performance test results of silicon based anode material provided in this embodiment are shown in Table 1.
Embodiment 7
The present embodiment provides a kind of silicon-based anode piece, the cathode coating of the silicon-based anode piece includes being coated on copper foil afflux
First coating on body and the second coating being coated in first coating.
The first coating includes active material, conductive agent and binder, and wherein active material is to aoxidize sub- silicon SiO0.6,
Conductive agent is graphite powder, and binder is sodium carboxymethylcellulose.In the first coating, the mass fraction of active material is
60%, the mass fraction of conductive agent is 10%, and the mass fraction of binder is 30%.
The second coating includes active material, conductive agent and binder, and wherein active material is artificial graphite, conductive agent
For graphite powder, binder is sodium carboxymethylcellulose.In the second coating, the mass fraction of active material is 60%, conductive
The mass fraction of agent is 30%, and the mass fraction of binder is 10%.The second coating surface is also containing lithium simple substance and lithium
Carbide, in silicon-based anode piece provided in this embodiment, the mass fraction of elemental lithium is 1%.
In the silicon-based anode piece, first coating with a thickness of 60 microns, second coating with a thickness of 30 microns, first applies
Layer double spread in copper foil current collector.
The preparation method of silicon-based anode piece provided in this embodiment is referring to embodiment 1.
The performance test results of silicon based anode material provided in this embodiment are shown in Table 1.
Comparative example 1
The cathode coating for the silicon-based anode piece that this comparative example provides is free of second coating, only contains first coating.Described
One coating includes active material, conductive agent and binder, and wherein active material is to aoxidize sub- silicon, and conductive agent is graphite powder, bonding
Agent is sodium carboxymethylcellulose.In the first coating, active material, the mass fraction of conductive agent and binder and embodiment 1
The first coating of the silicon-based anode piece of offer is identical.
Lithium simple substance (lithium powder) is also contained on the first coating surface for the silicon-based anode piece that this comparative example provides, and mentions in this comparative example
In the silicon-based anode piece of confession, the mass fraction of lithium is same as Example 1.
The of the silicon-based anode piece that the thickness of first coating and embodiment 1 provide in the silicon-based anode piece that this comparative example provides
One coating layer thickness is identical.
Referring to the preparation method of embodiment 1, difference is the preparation method for the silicon-based anode piece that this comparative example provides, not into
The operation of row step (2), and the behaviour of step (3) in embodiment 1 is directly carried out to the pole piece containing first coating that step (1) obtains
Make.
The performance test results for the silicon based anode material that this comparative example provides are shown in Table 1.
Test method
Anode pole piece preparation: 811 nickelic positive ternary materials (95%) and conductive agent (2%), binder (3%) are dispersed
It in NMP, is coated on aluminium foil after stirring mixing, eventually passes through dry, nipping process and obtain positive plate；
(poly- second/propylene is composite microporous with positive plate, diaphragm for the silicon-based anode piece that foregoing embodiments and comparative example are provided
Film) it is wound, it is carried out later into shell, fluid injection (1mol/L LiPF6+ EC+EMC), encapsulation, obtain lithium ion secondary battery, it is right
This secondary cell carries out energy density test in 0.5C/1C, voltage range 2.8V-4.2V under room temperature, in room temperature or 45 DEG C
Under the conditions of carry out cyclical stability test (actual conditions are shown in Table 1).Test result is as follows.
Table 1
Based on the above embodiments with comparative example it is found that silicon-based anode piece provided by the invention is because avoid containing silicon-based anode
The pole piece of material silica-base material during prelithiation is contacted with the direct of lithium metal, so embedding lithium is uniform, solves silicon substrate
Material directly contacts the denaturation of bring silica-base material, uneven embedding lithium, broken even pulverizing problem with lithium, and it is close to be obviously improved energy
Degree and cyclical stability.Contact point is reacted after comparative example does not use the solution of the present invention, silica-base material to contact with lithium simple substance
Comparatively fast, lead to the uneven of material granule structure, so that the adverse consequences such as Particle Breakage occur, the uneven embedding lithium product of formation
Stability is poor, and capacity reduces rapidly during following cycle.
The Applicant declares that the present invention is explained by the above embodiments method detailed of the invention, but the present invention not office
Be limited to above-mentioned method detailed, that is, do not mean that the invention must rely on the above detailed methods to implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of silicon-based anode piece, which is characterized in that the cathode coating of the silicon-based anode piece includes the on the collector
One coating and the second coating in first coating, the active material in the first coating includes silicon based anode material, institute
The active material stated in second coating does not include silicon based anode material, and lithium is contained on the second coating surface.
2. silicon-based anode piece according to claim 1, which is characterized in that the silicon based anode material includes silicon and/or oxygen
Change sub- silicon, preferably aoxidizes sub- silicon；
Preferably, the sub- chemistry of silicones formula of the oxidation is SiOx, wherein 0 < x < 1；
Preferably, the active material in the first coating further includes containing carbon negative pole material；
Preferably, the carbon containing negative electrode active material in the first coating includes graphite and/or amorphous carbon material；
Preferably, the graphite includes artificial graphite and/or natural graphite；
Preferably, the amorphous carbon material includes soft carbon and/or hard carbon；
Preferably, silicon based anode material and the mass ratio containing carbon negative pole material are 3:97-100:0 in the first coating；
Preferably, the active material in the second coating includes carbon containing negative electrode active material；
Preferably, the carbon containing negative electrode active material includes graphite and/or amorphous carbon material；
Preferably, the graphite includes artificial graphite and/or natural graphite；
Preferably, the amorphous carbon material includes soft carbon and/or hard carbon；
Preferably, the lithium that the second coating surface is contained is the compound of lithium simple substance and/or lithium, lithium in the compound of the lithium
Chemical valence be negative value；
Preferably, the compound of the lithium includes the carbide of lithium；
Preferably, the collector includes copper foil；
Preferably, the first coating with a thickness of 5-300 microns；
Preferably, the second coating with a thickness of 1-100 microns；
Preferably, in the silicon-based anode piece, the mass fraction of elemental lithium is 0.05-10%；
Preferably, first coating one side coating or double spread on a current collector.
3. silicon-based anode piece according to claim 1 or 2, which is characterized in that the first coating includes active material, leads
Electric agent and binder；
Preferably, the conductive agent include in graphite powder, active carbon, carbon black or acetylene black any one or at least two group
It closes；
Preferably, the binder includes polytetrafluoroethylene (PTFE), Kynoar, hydroxypropyl methyl cellulose, carboxymethyl cellulose
In sodium or butadiene-styrene rubber any one or at least two combination；
Preferably, in the first coating, the mass fraction of active material is 60-98.9%, and the mass fraction of conductive agent is
0.1-30%, the mass fraction of binder are 1-30%.
4. silicon-based anode piece according to claim 1-3, which is characterized in that the second coating includes active matter
Matter, conductive agent and binder；
Preferably, the conductive agent include in graphite powder, active carbon, carbon black or acetylene black any one or at least two group
It closes；
Preferably, the binder includes polytetrafluoroethylene (PTFE), Kynoar, hydroxypropyl methyl cellulose, carboxymethyl cellulose
In sodium or butadiene-styrene rubber any one or at least two combination；
Preferably, in the second coating, the mass fraction of active material is 60-98.9%, and the mass fraction of conductive agent is
0.1-30%, the mass fraction of binder are 1-30%.
5. a kind of preparation method of the silicon-based anode piece as described in claim any one of 1-4, which is characterized in that the method includes
Following steps:
(1) first coating is formed on a current collector with the first slurry coating containing silicon based anode material, obtain containing first coating
Pole piece；
(2) the second painting is formed in the first coating of step (1) pole piece with the second slurry for not including silicon based anode material
Layer, obtains the pole piece containing second coating；
(3) lithium is mixed in advance in step (2) the pole piece progress containing second coating, obtains the silicon-based anode piece.
6. preparation method according to claim 5, which is characterized in that the preparation method packet of step (1) first slurry
It includes: the active material, conductive agent and binder of formula ratio is mixed with solvent, obtain first slurry；
Preferably, the solvent includes water；
Preferably, in first slurry, the mass fraction of active material is 20-80%；
Preferably, in step (1), the method for forming first coating includes: that the first slurry is sprayed on collector to go forward side by side
Row drying；
Or slurry is coated on collector and is dried using transfer coater；
Preferably, the preparation method of step (2) second slurry includes: by the active material, conductive agent and bonding of formula ratio
Agent is mixed with solvent, obtains second slurry；
Preferably, the solvent includes water；
Preferably, in second slurry, the mass fraction of active material is 20-80%；
Preferably, in step (2), the method for forming second coating includes: to be sprayed on second coating in first coating simultaneously
It is dried；
Or slurry is coated on collector and is dried using transfer coater.
7. preparation method according to claim 5 or 6, which is characterized in that in step (3), further includes: in advance mix lithium it
Before, roll-in is carried out to the pole piece described in step (2) containing second coating；
Preferably, the pressure of the roll-in is 10-200 tons.
8. the preparation method according to any one of claim 5-7, which is characterized in that step (3) the pre- side for mixing lithium
Method includes: using lithium powder, and the pole piece containing second coating described in step (2) carries out trembling powder；
Alternatively, the pole piece containing second coating described in step (2) is rolled using lithium band.
9. the preparation method according to any one of claim 5-8, which is characterized in that the described method comprises the following steps:
(1) silicon based anode material of formula ratio, carbon based negative electrodes material, conductive agent and binder are mixed with solvent, obtains first
Slurry on a current collector by first slurry coating obtains the pole piece containing first coating after dry；
Wherein, in first slurry, the mass fraction of active material is 20-80%；
(2) active material not comprising silicon based anode material, conductive agent and the binder of formula ratio are mixed with solvent, obtains
Second slurry is coated in the first coating of step (1) pole piece by two slurries, obtains the pole containing second coating after dry
Piece；
Wherein, in second slurry, the mass fraction of active material is 20-80%；
(3) roll-in is carried out with 10-200 tons of pressure to the pole piece containing second coating described in step (2), and carries out mixing lithium in advance,
Obtain the silicon-based anode piece；
Wherein, the pre- method for mixing lithium includes being carried out trembling powder or being adopted in the pole piece containing second coating using lithium powder
Rolled with lithium band in the pole piece containing second coating.
10. a kind of lithium ion battery, which is characterized in that the lithium ion battery is negative comprising silicon substrate as claimed in claim 1 or 2
Pole piece.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011136028A1 (en) * | 2010-04-28 | 2011-11-03 | Semiconductor Energy Laboratory Co., Ltd. | Power storage device and method for manufacturing the same |
| US20120070741A1 (en) * | 2010-03-03 | 2012-03-22 | Amprius, Inc. | High capacity battery electrode structures |
| CN107528044A (en) * | 2017-07-25 | 2017-12-29 | 深圳市沃特玛电池有限公司 | A kind of lithium ion battery negative electrode and preparation method thereof |
| CN108550780A (en) * | 2018-03-22 | 2018-09-18 | 天津市捷威动力工业有限公司 | A kind of negative electrode of lithium ion battery single side prelithiation method using three-dimensional foil |
-
2019
- 2019-02-28 CN CN201910151505.0A patent/CN109888266A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120070741A1 (en) * | 2010-03-03 | 2012-03-22 | Amprius, Inc. | High capacity battery electrode structures |
| WO2011136028A1 (en) * | 2010-04-28 | 2011-11-03 | Semiconductor Energy Laboratory Co., Ltd. | Power storage device and method for manufacturing the same |
| CN107528044A (en) * | 2017-07-25 | 2017-12-29 | 深圳市沃特玛电池有限公司 | A kind of lithium ion battery negative electrode and preparation method thereof |
| CN108550780A (en) * | 2018-03-22 | 2018-09-18 | 天津市捷威动力工业有限公司 | A kind of negative electrode of lithium ion battery single side prelithiation method using three-dimensional foil |
Cited By (20)
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|---|---|---|---|---|
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| CN112786949A (en) * | 2019-11-06 | 2021-05-11 | 宁德时代新能源科技股份有限公司 | Secondary battery, battery module, battery pack and device containing same |
| WO2021088718A1 (en) * | 2019-11-06 | 2021-05-14 | 宁德时代新能源科技股份有限公司 | Secondary battery, and battery module, battery pack and device containing same |
| CN114982007B (en) * | 2020-03-27 | 2024-03-29 | 株式会社Lg新能源 | Method for manufacturing negative electrode |
| CN114982007A (en) * | 2020-03-27 | 2022-08-30 | 株式会社Lg新能源 | Method for manufacturing negative electrode |
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