CN109786706A - Negative electrode material and preparation method thereof, cathode and battery - Google Patents
Negative electrode material and preparation method thereof, cathode and battery Download PDFInfo
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- CN109786706A CN109786706A CN201910045146.0A CN201910045146A CN109786706A CN 109786706 A CN109786706 A CN 109786706A CN 201910045146 A CN201910045146 A CN 201910045146A CN 109786706 A CN109786706 A CN 109786706A
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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 present invention provides negative electrode material and preparation method thereof, cathode and batteries.Wherein, the method for preparing negative electrode material includes: by silicon particle and dispersant, to form the first mixed liquor；Surfactant, the first solvent and carbon source are mixed, to form the second mixed liquor；First mixed liquor is mixed with second mixed liquor, and obtained mixture is successively dried, is roasted, to obtain the negative electrode material.This method is simple, convenient, it is easy to accomplish, the head of the negative electrode material of acquisition is imitated, specific capacity and cycle performance are preferable.
Description
Technical field
The present invention relates to battery technology fields, specifically, being related to negative electrode material and preparation method thereof, cathode and battery.
Background technique
Currently, silicon is theoretical lithium storage content (4200mAh/g) highest material, it is conventional graphite cathode (372mAh/g)
Ten times, and be far longer than the specific capacity of various nitride and oxide, in addition its resourceful, no pollution to the environment, be lithium from
The research hotspot of sub- cell negative electrode material.But in charge and discharge process, silicon and lithium form Li under complete state of lithiation4.4Si is closed
Gold, volume expansion are about 400%, and this volume change destroys electrode structure stability, and Yi Yinqi electrode structure collapses, causes
The rapid decaying of battery capacity hinders application of the silicon based anode material in commercial li-ion battery.
Thus, current negative electrode material still has much room for improvement.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, of the invention
One purpose is to propose a kind of simple, convenient, it is easy to accomplish or the side of the preparation negative electrode material of lower production costs
Method, the negative electrode material structure obtained using this method is more stable, the battery specific capacity being prepared using the negative electrode material is higher,
It is preferable that head imitates higher or cycle performance.
In one aspect of the invention, the present invention provides a kind of methods for preparing negative electrode material.Reality according to the present invention
Example is applied, this method comprises: by silicon particle and dispersant, to form the first mixed liquor；By surfactant, the first solvent
It is mixed with carbon source, to form the second mixed liquor；First mixed liquor is mixed with second mixed liquor, and will be acquired
Mixture be successively dried, roast, to obtain the negative electrode material.Inventors have found that this method is easy to operate, side
Just, it is easy to accomplish, it will be mixed again with the second mixed solution containing surfactant after silicon particle dispersion, silicon can be made
Grain is uniformly dispersed in carbon source, and silicon particle can be uniformly dispersed in carbon material (i.e. in the negative electrode material obtained after roasting
Carbon source after carbonization) surface on, hardly there is the phenomenon that silicon particle reunion, and on at least partly outer surface of silicon particle
It is coated with carbon shell, so that the structure of negative electrode material is more stable, can effectively inhibit the expansion of silicon particle, effectively reduce in charge and discharge
The dusting of silicon in electric process weakens the growth of SEI film, effectively extends the service life of negative electrode material, and then effectively improves utilization
First effect, specific capacity and the cycle performance for the battery that the negative electrode material is prepared.
According to an embodiment of the invention, the mass ratio of the silicon particle and the dispersing agent is 1:20-1:5.Silicon as a result,
Particle can be more adequately dispersed in dispersing agent, be conducive to subsequent silicon particle and be uniformly dispersed in carbon source, can be effective
Reduce the reunion of silicon particle in negative electrode material.
According to an embodiment of the invention, the gross mass based on the negative electrode material, the content of the silicon particle is 5wt%-
30wt%.The content of silicon particle is more appropriate as a result, and what is be distributed in carbon material is relatively uniform, there's almost no agglomeration,
Be conducive to improve the chemical property of negative electrode material.
According to an embodiment of the invention, the partial size of the silicon particle is 50 nanometers -300 nanometers.The partial size of silicon particle as a result,
Size is more appropriate, and specific surface area is larger, is conducive to insertion and the desorption of lithium ion so that the chemical property of negative electrode material compared with
It is good.
According to an embodiment of the invention, described mix surfactant, the first solvent and carbon source includes: by the surface
Activating agent is mixed with first solvent, to obtain third mixed liquor；The carbon source is mixed with the third mixed liquor, with
Just second mixed liquor is obtained.Carbon source can be uniformly dispersed in third mixed liquor as a result, and then it is equal to be conducive to silicon particle
Even is dispersed in carbon source, so that the structure of negative electrode material is more stable, chemical property is preferable.
According to an embodiment of the invention, the formation third mixed liquor further include: by the surfactant and binder
It is added in first solvent jointly, to obtain the third mixed liquor.Third mixed liquor is suspension as a result, and surface is living
Property agent dispersion it is more uniform, be more conducive to uniformly dispersing carbon source and silicon particle, be more advantageous to so that negative electrode material
Middle silicon particle is dispersed on the surface of carbon material, and then effectively avoids the reunion of silicon particle, so that the structure of negative electrode material
It is more stable, chemical property is preferable.
According to an embodiment of the invention, the mass ratio of the surfactant, the carbon source and the binder is
(0.01-0.1):1:(0.01-0.3).The mixing of third mixed liquor is more uniform as a result, is more conducive to carbon source and silicon
Evengranular dispersion, and the addition of surfactant can not only allow silicon particle to be uniformly dispersed in carbon source, but also can be with
Play the role of template, orderly pore structure can be left in carbon-coating after roasting removes, can inhibit silicon deviate from lithium ion/
Volume expansion in telescopiny.
According to an embodiment of the invention, the surfactant is selected from polyvinylpyrrolidone, polyethylene oxide-polycyclic oxygen
Propane-polyethylene oxide triblock copolymer and polyoxyethylene-poly-oxypropylene polyoxyethylene amphiphilic block copolymer.As a result,
Silicon particle can be made to disperse relatively uniform, be conducive to the structural stability for improving negative electrode material, and then cathode can be improved
The chemical property of material.
According to an embodiment of the invention, the binder includes carboxymethyl cellulose, polyethylene glycol, polytetrafluoroethylene (PTFE), sea
At least one of mosanom polyacrylic acid.The source of binder is relatively broad as a result, and price is lower, is conducive to third is molten
Liquid becomes suspension, and the dispersion of surfactant is more uniform in third solution, and then is conducive to the evenly dispersed of carbon source, in turn
Dispersing uniformity of the silicon particle in carbon source can be improved.
According to an embodiment of the invention, the carbon source be selected from graphite, expanded graphite, graphene, doped graphene, carbon pipe with
And at least one of crystalline flake graphite.Carbon source source is relatively broad as a result, and price is lower, and the electric conductivity after being carbonized is preferable,
So that the ability of negative electrode material transmission electronics is stronger, be conducive to improve the battery being prepared using the negative electrode material first effect,
Specific capacity and cycle performance.
According to an embodiment of the invention, it includes: in stirring bar that first mixed liquor is mixed with second mixed liquor
First mixed liquor is added dropwise in second mixed liquor under part.What silicon particle can be more uniform as a result, is dispersed in
In carbon source, it is more conducive to improving the uniformity of the dispersion of silicon particle in negative electrode material, reduces the better effect that silicon particle is reunited,
Be conducive to improve the chemical property for the battery being prepared using the negative electrode material.
According to an embodiment of the invention, being by the drop speed that first mixed liquor is added dropwise in second mixed liquor
0.01ml/s-0.005ml/s.The first mixed liquor mixes more uniform with the second mixed liquor as a result, is conducive to silicon particle is equal
Even is dispersed in carbon source, and silicon particle there's almost no agglomeration, and then improve the electricity being prepared using the negative electrode material
The better effect of the first effect in pond, specific capacity and cycle performance.
In another aspect of this invention, the present invention provides a kind of negative electrode materials.According to an embodiment of the invention, the cathode
Material is prepared using mentioned-above method.Inventors have found that the structure of negative electrode material is simple, is easily achieved, tie
Structure is more stable, and chemical property is preferable, utilizes first effect, specific capacity and the cyclicity of the battery that the negative electrode material is prepared
Can preferably, service life is longer, and higher specific capacity and cycle performance, market are able to maintain in longer use process
Competitiveness is stronger, the consumption experience for the consumer that is content with very little.
In another aspect of this invention, the present invention provides a kind of cathode.According to an embodiment of the invention, the cathode includes
Mentioned-above negative electrode material.Inventors have found that the first effect of the cathode, specific capacity and cycle performance are preferable, service life compared with
It is long, and higher specific capacity and cycle performance are able to maintain in longer use process, the market competitiveness is stronger, is easy to full
The consumption experience of sufficient consumer.
In another aspect of this invention, the present invention provides a kind of batteries.According to an embodiment of the invention, the battery pack
It includes: mentioned-above cathode；Anode；Diaphragm, the diaphragm setting is between the anode and the cathode；Electrolyte, it is described
At least part of anode, at least part of at least part of the cathode and the diaphragm are immersed in the electrolyte
In.Inventors have found that the battery structure is simple, is easily achieved, price is lower, and head effect, specific capacity and cycle performance are preferable, makes
With lasting a long time, and higher specific capacity and cycle performance are able to maintain in longer use process, the market competitiveness compared with
By force, be content with very little the consumption experience of consumer.
Detailed description of the invention
Fig. 1 is the method flow schematic diagram that negative electrode material is prepared in one embodiment of the invention.
Fig. 2 is that the method flow for mixing surfactant, the first solvent and carbon source in one embodiment of the invention is illustrated
Figure.
Fig. 3 is the scanning electron microscope (SEM) photograph of the negative electrode material obtained in the embodiment of the present invention 1.
Fig. 4 is the scanning electron microscope (SEM) photograph of the negative electrode material obtained in the embodiment of the present invention 2.
Fig. 5 and Fig. 6 is the scanning electron microscope (SEM) photograph of the negative electrode material obtained in the embodiment of the present invention 3.
Fig. 7 is the scanning electron microscope (SEM) photograph of the negative electrode material obtained in comparative example 1.
Specific embodiment
The embodiment of the present invention is described below in detail.The embodiments described below is exemplary, and is only used for explaining this hair
It is bright, and be not considered as limiting the invention.Particular technique or condition are not specified in embodiment, according to text in the art
It offers described technology or conditions or is carried out according to product description.Reagents or instruments used without specified manufacturer,
For can be with conventional products that are commercially available.
In one aspect of the invention, the present invention provides a kind of methods for preparing negative electrode material.Reality according to the present invention
Example is applied, referring to Fig.1, this method comprises:
S100: by silicon particle and dispersant, to form the first mixed liquor.
According to an embodiment of the invention, the mass ratio of the silicon particle and the dispersing agent is 1:20-1:5, such as 1:20,1:
19,1:18,1:17,1:16,1:15,1:14,1:13,1:12,1:11,1:10,1:9,1:8,1:7,1:6 or 1:5 etc..As a result,
Silicon particle can be more adequately dispersed in dispersing agent, be conducive to subsequent silicon particle and be uniformly dispersed in carbon source, Ke Yiyou
Effect reduces the reunion of silicon particle in negative electrode material.Relative to above-mentioned quality than range, when the mass ratio mistake of silicon particle and dispersing agent
When low, then the dispersion effect of silicon particle is relatively preferable, but is detrimental to industrialized production, when the mass ratio of silicon particle and dispersing agent
When excessively high, then the dispersion effect of silicon particle is not relatively good enough, and silicon particle is extremely easy to reunite, and particle size is grown up, to influence negative
The chemical property of pole material.
According to an embodiment of the invention, the partial size of the silicon particle be 50 nanometers -300 nanometers (such as 50 nanometers, 100 receive
Rice, 150 nanometers, 200 nanometers, 250 nanometers, 300 nanometers etc.).The particle size of silicon particle is more appropriate as a result, specific surface area
It is larger, be conducive to insertion and the desorption of lithium ion, so that the chemical property of negative electrode material is preferable.Relative to above-mentioned partial size model
It encloses, when the partial size of silicon particle is excessive, then silicon particle is larger, is influenced then relatively more greatly, not with circulation by bulk effect
Disconnected extension always exists material expansion dusting, the capacity of material is made to show biggish fluctuation, and the continuous powder of material
Change, the new SEI film of new exposed Surface Creation consumes a large amount of lithium ion, drastically declines so that capacity is opposite；Work as silicon particle
Partial size it is too small when, due to quantum size effect, silicon particle is easy to reunite, and dispersion effect is relatively bad, the diffusion to lithium ion
Relatively serious obstruction is constituted, Li is lengthened+Diffusion length.Can be because silicon particle be assembled in charge and discharge process, volume expansion,
Lead to silicon particle rupture, be crushed, reduces the capacity of material.
According to an embodiment of the invention, dispersing agent is selected from least one of dehydrated alcohol, isopropanol, deionized water.By
This, dispersing agent is from a wealth of sources, and price is lower, and the effect for dispersing silicon particle is preferable.
It can be with according to an embodiment of the invention, silicon particle is dispersed in the concrete operation step in dispersing agent are as follows:
By silicon particle and dispersant, by obtained mixed liquor ultrasonic disperse 30min-4h (such as 30min, 1h,
1.5h, 2h, 2.5h, 3h, 3.5h, 4h etc.), obtain the first mixed liquor.
S200: surfactant, the first solvent and carbon source are mixed, to form the second mixed liquor.
According to an embodiment of the invention, the addition of surfactant is so that carbon source and the dispersion ratio of silicon particle are more uniform
Principle is that nanoparticle has skin effect and bulk effect, since its special surface texture is easy to reunite, surface-active
Agent is not only used as template in the early stage, but also nano grain surface can be allowed by wet with solvent, to prevent silicon nanoparticle rapidly
Reunite.
According to an embodiment of the invention, the surfactant is selected from polyvinylpyrrolidone (PVP), polyethylene oxide-
Polypropylene oxide-polyethylene oxide triblock copolymer (P123) and polyoxyethylene-poly-oxypropylene polyoxyethylene amphiphilic block
Copolymer (F127).Material source is extensive as a result, and price is lower, silicon particle can be made to disperse relatively uniform, be conducive to mention
The structural stability of high negative electrode material, and then the chemical property of negative electrode material can be improved.
According to an embodiment of the invention, the carbon source be selected from graphite, expanded graphite, graphene, doped graphene, carbon pipe with
And at least one of crystalline flake graphite.Carbon source source is relatively broad as a result, and price is lower, and the electric conductivity after being carbonized is preferable,
So that the ability of negative electrode material transmission electronics is stronger, chemical property is preferable, is conducive to raising and is prepared into using the negative electrode material
First effect, specific capacity and the cycle performance of the battery arrived.
According to an embodiment of the invention, the first solvent can be for deionized water, ethyl alcohol etc., material source is extensive, price compared with
Low, the effect of the components such as dispersion carbon source is preferable.
According to an embodiment of the invention, referring to Fig. 2, described mix surfactant, the first solvent and carbon source includes:
S210: the surfactant is mixed with first solvent, to obtain third mixed liquor.
According to an embodiment of the invention, in order to obtain the relatively uniform third mixed liquor of mixing, by surfactant with
After the mixing of first solvent, mixed liquor can be ultrasonically treated, thus, it is possible to which surfactant is uniformly dispersed in the
In three mixed liquors.
According to an embodiment of the invention, in order to enable more uniform, the formation third mixing of third mixed liquor mixing
Liquid further include: the surfactant and binder are added jointly in first solvent, to obtain the third mixing
Liquid.As a result, third mixed liquor be suspension, surfactant-dispersed it is more uniform, be more conducive to subsequent carbon source and silicon
Evengranular dispersion is more advantageous to so that silicon particle is dispersed in the surface of carbon material in the negative electrode material finally obtained
On, and then the reunion of silicon particle is effectively avoided, so that the structure of negative electrode material is more stable, chemical property is preferable.
According to an embodiment of the invention, the binder includes carboxymethyl cellulose (CMC), polyethylene glycol, polytetrafluoroethyl-ne
At least one of alkene (PTFE), sodium alginate polyacrylic acid (PAA).The source of binder is relatively broad as a result, price compared with
It is low, be conducive to becoming third solution into suspension, the dispersion of surfactant is more uniform in third solution, and then is conducive to carbon
Source it is evenly dispersed, and then dispersing uniformity of the silicon particle in carbon source can be improved.
According to an embodiment of the invention, the mass ratio of the surfactant, the carbon source and the binder is
(0.01-0.1): 1:(0.01-0.3), in other words, the quality of surfactant is the quality of carbon source in the second mixed liquor
1wt%-10wt% (such as 1wt%, 2wt%, 4wt%, 5wt%, 5.5wt%, 7wt%, 7.5wt%, 8wt%, 9wt%,
10wt% etc.), the quality of binder is the 1wt%-30% of the quality of carbon source in the second mixed liquor, (such as 1wt%, 5wt%,
10wt%, 15wt%, 20wt%, 25wt%, 30wt% etc.).The mixing of third mixed liquor is more uniform as a result, advantageously
Uniformly disperse in subsequent carbon source and silicon particle.Relative to above-mentioned quality than range, when the quality of surfactant and carbon source
Than it is excessively high when, then after baking remove surfactant after, the hole retained in negative electrode material is comparatively small and more, is unfavorable for lithium
The intercalation/deintercalation of ion, so that the chemical property of negative electrode material is influenced, when the mass ratio of surfactant and binder is too low
When, then comparatively will cause carbon source cannot form stable solution, and it is uneven to have in turn resulted in dispersion of the silicon particle in carbon source
It is even, it be easy to cause a large amount of reunions of silicon particle；The content of above-mentioned binder is more appropriate, is conducive to the evenly dispersed of carbon source, will
The cathode that silicon particle can make silicon particle be uniformly dispersed in carbon source, and then obtain after firing after mixing with carbon source
Silicon particle can be uniformly dispersed on the surface of carbon material in material, almost without agglomeration generation.Relative to above-mentioned matter
Amount is than range, when the mass ratio of binder and carbon source is excessive, is then easy so that viscosity is relatively excessive, with the first mixture solution
Effectively silicon particle cannot be made to disperse when mixing, be easy to cause agglomeration, when the mass ratio of binder and carbon source is too small, then
It is opposite to be not easy to form stable suspension, it is also easy to produce lamination, is unfavorable for evenly dispersed.
S220: the carbon source is mixed with the third mixed liquor, to obtain second mixed liquor.
According to an embodiment of the invention, the specific steps that carbon source is mixed with third solution can be with are as follows: under agitation,
Carbon source is slowly added in third mixed liquor, addition finish after continue stir 1h-12h (such as 1h, 2h, 3h, 4h, 5h, 6h, 7h,
8h, 9h, 10h, 11h, 12h etc.) form the second mixed liquor.It is simple, convenient as a result, carbon source in the second mixed liquor of acquisition
The comparison of dispersion sufficiently, uniformly, and then is conducive to silicon particle and is uniformly dispersed in carbon source, is conducive to the progress of subsequent step.
S300: first mixed liquor is mixed with second mixed liquor, and obtained mixture is successively carried out
Dry, roasting, to obtain the negative electrode material.
According to an embodiment of the invention, it includes: in stirring bar that first mixed liquor is mixed with second mixed liquor
First mixed liquor is added dropwise in second mixed liquor under part.What silicon particle can be more uniform as a result, is dispersed in
In carbon source, it is more conducive to improving the uniformity of the dispersion of silicon particle in negative electrode material, reduces the better effect that silicon particle is reunited,
Be conducive to improve the chemical property of negative electrode material.
According to an embodiment of the invention, being by the drop speed that first mixed liquor is added dropwise in second mixed liquor
0.01ml/s-0.005ml/s, as 0.01ml/s, 0.009ml/s, 0.008ml/s, 0.007ml/s, 0.006ml/s,
0.005ml/s etc..The first mixed liquor mixes more uniform with the second mixed liquor as a result, is conducive to uniformly divide silicon particle
It is dispersed in carbon source, silicon particle there's almost no agglomeration, and then improve the head for the battery being prepared using the negative electrode material
The better effect of effect, specific capacity and cycle performance.Then, it is unfavorable for industry when drop speed is too low relative to above-mentioned drop speed range
Metaplasia produces；When drop speed is excessively high, then drop rate is too fast, then silicon particle is be easy to cause to reunite when carbon source is uncoated complete one
It rises, be easy to cause the incomplete and agglomeration of cladding.
According to an embodiment of the invention, the specific steps that the first mixed liquor is mixed with the second mixed liquor can be with are as follows: stirring
Under the conditions of mixing, the first mixed liquor is added dropwise in third mixed liquor, be added dropwise after continue stir 1h-12h (such as 1h,
2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h etc.), so that the first mixed liquor and the second mixed liquor are sufficiently mixed
It is even.
According to an embodiment of the invention, the method for above-mentioned drying includes, stirring is evaporated, convection oven is dry, freeze-drying with
And at least one of vacuum drying.Thus, it is possible to effectively that the mixture of the first mixed liquor and the second mixed liquor is dry.Below
Dry method is illustrated so that stirring is evaporated as an example: mixture is put into 50 DEG C -120 DEG C (such as 50 DEG C, 60 DEG C, 70 DEG C, 80
DEG C, 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C etc.) water-bath in stir and be evaporated.
According to an embodiment of the invention, roasting after drying finishes to the solid of acquisition, the temperature of roasting is 600
DEG C -1000 DEG C (such as 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C, 900 DEG C, 950 DEG C, 1000 DEG C etc.), the time
For 1h-10h (such as 1h, 2h, 3h, 4h, 6h, 5h, 6h, 7h, 8h, 9h, 10h etc.), and roasting is in inert atmosphere (such as argon
Gas, nitrogen etc.) under carry out.Thus, it is possible to form the carbon material for having certain structure, the electric conductivity of carbon material is preferable, passes
Sub ability of transmitting electricity is stronger, and silicon particle is uniformly dispersed in the surface of carbon material, wraps on at least partly surface of silicon particle
It is covered with carbon shell, can effectively inhibit the expansion of silicon particle, weakens the growth of SEI film, effectively extends the service life of negative electrode material,
So that the battery being prepared using the negative electrode material is able to maintain preferably first effect, specific capacity in a longer period of time and followed
Ring performance.Inertia phase SiC can be generated relative to above-mentioned maturing temperature and calcining time, when maturing temperature is excessively high, inertia does not have mutually
Lithium storage content, opposite that specific capacity is caused to decline, calcining time is too long, and agglomeration easily occurs in silicon particle, not only influences cathode material
The electric conductivity of material, while lithium ion diffusion path lengthens, the insertion and abjection that part lithium ion can not be successfully lead to negative electrode material
Discharge capacity is relatively low for the first time；When maturing temperature is too low, first is that the carbonization of carbon source is relatively incomplete, second is that as pyrolysis is anti-
It should carry out, silicon particle surface begins with deposit attachment, and negative electrode material surface is still relatively rough, and specific surface area is larger, forms SEI
Film needs to consume more lithium ion, causes coulombic efficiency relative reduction, and calcining time is too short, then carbon source carbonization is relatively endless
Entirely, lead to electric conductivity relative drop.
According to an embodiment of the invention, the gross mass based on the negative electrode material, the content of the silicon particle is 5wt%-
30wt% (such as 5wt%, 5.5wt%, 6wt%, 6.5wt%, 7wt%, 7.5wt%, 8wt%, 8.5wt%, 9wt%,
9.5wt%, 10wt%, 10.5wt%, 11wt%, 11.5wt%, 12wt%, 12.5wt%, 13wt%, 13.5wt%,
14wt%, 14.5wt%, 15wt%, 15.5wt%, 16wt%, 16.5wt%, 17wt%, 17.5wt%, 18wt%,
18.5wt%, 19wt%, 19.5wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%,
27wt%, 28wt%, 29wt%, 30wt% etc.).The content of silicon particle is more appropriate as a result, the comparison being distributed in carbon material
Uniformly, it there's almost no agglomeration, be conducive to the chemical property for improving negative electrode material.Relative to above-mentioned content range, when
When the too high levels of silicon particle, first is that silicon particle is relatively easily reunited, lead to the chemical property of negative electrode material relatively not
Good, second is that bulk effect becomes obviously in electrochemical reaction process, material structure is relatively easily destroyed, and causes cycle performance opposite
Decline；Since silicon is the important component in negative electrode material, the most capacity of negative electrode material all derives from silicon, works as silicone content
When too low, the capacity of negative electrode material is relatively low.
According to an embodiment of the invention, the method for above-mentioned preparation negative electrode material is simple, convenient, it is easy to accomplish, by silicon
It is mixed again with the second mixed solution containing surfactant after particle dispersion, silicon particle can be made to be uniformly dispersed in carbon
In source, silicon particle can be uniformly dispersed in the table of carbon material (carbon source after being carbonized) in the negative electrode material of acquisition after roasting
On face, hardly there is the phenomenon that silicon particle reunion, and carbon shell is coated on at least partly outer surface of silicon particle, so that negative
The structure of pole material is more stable, can effectively inhibit the expansion of silicon particle, effectively reduce the dusting of the silicon in charge and discharge process,
Weaken the growth of SEI film, effectively extend the service life of negative electrode material, and then effectively improves and be prepared using the negative electrode material
Battery first effect, specific capacity and cycle performance, some data show the first effect up to 90% or more of batteries, discharge capacity
Up to 900mAh/g or more.
In another aspect of this invention, the present invention provides a kind of negative electrode materials.According to an embodiment of the invention, the cathode
Material is prepared using mentioned-above method.Inventors have found that the structure of negative electrode material is simple, is easily achieved, tie
Structure is more stable, and the head for the battery being prepared using the negative electrode material is imitated, specific capacity and cycle performance are preferable, service life
It is longer, and higher specific capacity and cycle performance are able to maintain in longer use process, some data show battery
Head effect up to 90% or more, for discharge capacity up to 900mAh/g or more, the market competitiveness is stronger, and the consumer's that is content with very little disappears
Take experience.
In another aspect of this invention, the present invention provides a kind of cathode.According to an embodiment of the invention, the cathode includes
Mentioned-above negative electrode material.Inventors have found that the first effect of the cathode, specific capacity and cycle performance are preferable, service life compared with
It is long, and higher specific capacity and cycle performance are able to maintain in longer use process, the market competitiveness is stronger, is easy to full
The consumption experience of sufficient consumer.
According to an embodiment of the invention, above-mentioned cathode processing includes that can also include except mentioned-above negative electrode material
Binder (such as benzene rubber etc.), conductive agent (such as acetylene black etc.), thickener (such as carboxymethyl cellulose etc.) and afflux
Body (such as copper foil etc.) etc..
In another aspect of this invention, the present invention provides a kind of batteries.According to an embodiment of the invention, the battery pack
It includes: mentioned-above cathode；Anode；Diaphragm, the diaphragm setting is between the anode and the cathode.Inventors have found that
The battery structure is simple, is easily achieved, and price is lower, and head effect, specific capacity and cycle performance are preferable, and service life is longer, and
Higher specific capacity and cycle performance are able to maintain in longer use process, the market competitiveness is stronger, is content with very little and disappears
The consumption experience of the person of expense.
According to an embodiment of the invention, the material for forming anode may include: positive electrode (such as cobalt acid lithium etc.), conduction
Agent (such as acetylene black etc.), binder (such as Kynoar etc.) and collector (such as copper foil etc.) etc..According to the present invention
Embodiment, the material for forming diaphragm may include polyethylene, polypropylene etc..According to an embodiment of the invention, electrolyte includes
Solute and solvent, wherein the material for forming solvent includes propene carbonate, ethylene carbonate etc., and the material for forming solute includes
Lithium hexafluoro phosphate, LiBF4 etc..
According to an embodiment of the invention, above-mentioned battery other than including the positive electrode, the negative electrode and the separator, can also include outer
Shell, electrolyte (electrolyte, gel state electrolyte or the solid electrolyte of such as liquid) etc., no longer excessively repeat herein.According to
The embodiment of the present invention, above-mentioned battery can be lithium ion battery etc..
Embodiments herein is described below.
Embodiment
The negative electrode material prepared in following embodiment is assembled into progressive after lithium ion battery in the following way
It can test.
Pole piece preparation: by active material, acetylene black, binder (PAA and SBR mass ratio 3:5) according to the quality of 90:5:5
Than being tuned into slurry, it is coated uniformly on copper foil, copper foil is then then taken out into pole piece in 70 DEG C of air dry oven dry 4h, use
Pole piece is cut into the disk of diameter 12mm by sheet-punching machine, is weighed after hydraulic press tabletting.Pole piece after weighing continues to be put into vacuum
In baking oven, 70 DEG C of holding 10h remove traces of moisture.Pole piece is transferred in glove box after being cooled to room temperature, it is to be assembled.
Battery preparation: being to electrode, diameter 16mm, diaphragm Celgard2500, diameter 16mm, electrolyte with lithium piece
Using EC+DEC+EMC (v/v/v=1/1/1) mixed system of the lithium hexafluoro phosphate containing 1mol/L.All operating process are all being full of
It is carried out in the glove box of high-purity argon gas atmosphere.The performance test methods of lithium ion battery: charge-discharge test is using Lan electricity electricity
Pond test macro.Constant current charge-discharge voltage range 0.01-2.5V, the specific steps are as follows:
Embodiment 1:
The preparation of negative electrode material:
(1) 1g silicon particle (100nm) is dissolved in 10ml dehydrated alcohol, ultrasonic disperse 2h, forms solution A；
(2) weigh 0.04g F127,0.4g CMC is dissolved in the deionized water of 50ml, ultrasonic 1h dissolves to form solution B；
(3) 4g graphite is weighed, is slowly added into solution B under agitation and stirs 3h formation solution C；
(4) under agitation, solution A is added dropwise in solution C, drop speed is 0.01ml/s, is added dropwise subsequent
Continuous stirring 2h forms solution D；
(5) solution D is put into stir in 70 DEG C of water-baths and is evaporated, then risen in a nitrogen atmosphere with 5 DEG C/min rate
800 DEG C of roasting 4h.
In the present embodiment, the scanning electron microscope (SEM) photograph of negative electrode material can refer to Fig. 3, and the first effect of lithium ion battery is 85%, electric discharge
Specific capacity is 750mAh/g, cycle performance 500mA, and recycling 30 weeks conservation rates is 85%.
Embodiment 2:
The preparation of negative electrode material:
(1) 0.5g silicon particle (150nm) is dissolved in 10ml dehydrated alcohol, ultrasonic disperse 3h, forms solution A；
(2) weigh 0.09g P123,0.9g PAA is dissolved in the deionized water of 50ml, ultrasonic 2h dissolves to form solution B；
(3) 4.5g graphene is weighed, is slowly added into solution B under agitation and stirs 2h formation solution C；
(4) under agitation, solution A is added dropwise in solution C, drop speed is 0.01ml/s, is added dropwise subsequent
Continuous stirring 2h forms solution D；
(5) solution D is put into stir in 70 DEG C of water-baths and is evaporated, then risen in a nitrogen atmosphere with 2 DEG C/min rate
900 DEG C of roasting 2h.
In the present embodiment, the scanning electron microscope (SEM) photograph of negative electrode material can refer to Fig. 4, and the first effect of lithium ion battery is 89%, electric discharge
Specific capacity is 580mAh/g, cycle performance 500mA, and recycling 50 weeks conservation rates is 87%.
Embodiment 3:
The preparation of negative electrode material:
(1) 3g silicon particle (150nm) is dissolved in 20ml dehydrated alcohol, ultrasonic disperse 3h, forms solution A；
(2) weigh 0.07g F127,0.07gCMC is dissolved in the deionized water of 85ml, ultrasonic 2h dissolves to form solution B；
(3) 7g graphene is weighed, is slowly added into solution B under agitation and stirs 2h formation solution C；
(4) under agitation, solution A is added dropwise in solution C, drop speed is 0.005ml/s, is added dropwise subsequent
Continuous stirring 2h forms solution D；
(5) solution D is put into stir in 70 DEG C of water-baths and is evaporated, then risen in a nitrogen atmosphere with 2 DEG C/min rate
900 DEG C of roasting 2h.
In the present embodiment, the scanning electron microscope (SEM) photograph of negative electrode material is shown in Fig. 5 and Fig. 6, and the first effect of lithium ion battery is 90%, electric discharge
Specific capacity is 900mAh/g, and cycle performance is that 50 weeks conservation rates are recycled under 500mA is 90%.
Embodiment 4:
The preparation of negative electrode material:
(1) 1g silicon particle (50nm) is dissolved in 20ml isopropanol, ultrasonic disperse 3h, forms solution A；
(2) weigh 0.19g PVP, 0.19g polyethylene glycol is dissolved in the deionized water of 200ml, ultrasonic 2h dissolve to be formed it is molten
Liquid B；
(3) 19g doped graphene is weighed, is slowly added into solution B under agitation and stirs 1h formation solution C；
(4) under agitation, solution A is added dropwise in solution C, drop speed is 0.01ml/s, is added dropwise subsequent
Continuous stirring 12h forms solution D；
(5) solution D is put into stir in 70 DEG C of water-baths and is evaporated, then risen in a nitrogen atmosphere with 2 DEG C/min rate
1000 DEG C of roasting 10h.
In the present embodiment, in negative electrode material silicon particle surface-the first effect of lithium ion battery is 87%, specific discharge capacity is
400mAh/g, cycle performance are that 50 weeks conservation rates are recycled under 500mA is 85%.
Embodiment 5:
The preparation of negative electrode material:
(1) 1g silicon particle (300nm) is dissolved in 20ml isopropanol, ultrasonic disperse 3h, forms solution A；
(2) weigh 0.09g PVP, 0.45g PTFE is dissolved in the deionized water of 20ml, ultrasonic 2h dissolves to form solution B；
(3) 9g crystalline flake graphite is weighed, is slowly added into solution B under agitation and stirs 12h formation solution C；
(4) under agitation, solution A is added dropwise in solution C, drop speed is 0.01ml/s, is added dropwise subsequent
Continuous stirring 1h forms solution D；
(5) solution D is put into stir in 70 DEG C of water-baths and is evaporated, then risen in a nitrogen atmosphere with 2 DEG C/min rate
900 DEG C of roasting 1h.
In the present embodiment, the first effect of lithium ion battery is 86%, specific discharge capacity 500mAh/g, and cycle performance is
It is 85% that 50 weeks conservation rates are recycled under 500mA.
Embodiment 6:
The preparation of negative electrode material:
(1) 1.2g silicon particle (200nm) is dissolved in 24ml isopropanol, ultrasonic disperse 3h, forms solution A；
(2) it weighs 0.068g F127,1.02g PTFE, be dissolved in the deionized water of 20ml, ultrasonic 2h dissolves to form solution
B；
(3) 6.8g expanded graphite is weighed, is slowly added into solution B under agitation and stirs 6h formation solution C；
(4) under agitation, solution A is added dropwise in solution C, drop speed is 0.004ml/s, is added dropwise subsequent
Continuous stirring 6h forms solution D；
(5) solution D is freeze-dried, 850 DEG C of roasting 6h is then risen to 2 DEG C/min rate in a nitrogen atmosphere.
In the present embodiment, the first effect of lithium ion battery is 89%, specific discharge capacity 650mAh/g, and cycle performance is
It is 85% that 30 weeks conservation rates are recycled under 500mA
Embodiment 7:
The preparation of negative electrode material:
(1) 1g silicon particle (150nm) is dissolved in 20ml deionized water, ultrasonic disperse 3h, forms solution A；
(2) it weighs 0.09g P123, be dissolved in the deionized water of 20ml, ultrasonic 2h dissolves to form solution B；
(3) 9g graphene is weighed, is slowly added into solution B under agitation and stirs 6h formation solution C；
(4) under agitation, solution A is added dropwise in solution C, drop speed is 0.005ml/s, is added dropwise subsequent
Continuous stirring 6h forms solution D；
(5) solution D is freeze-dried, 950 DEG C of roasting 6h is then risen to 2 DEG C/min rate in a nitrogen atmosphere.
In the present embodiment, the first effect of lithium ion battery is 80%, specific discharge capacity 450mAh/g, and cycle performance is
It is 80% that 30 weeks conservation rates are recycled under 500mA
Embodiment 8:
The preparation of negative electrode material:
(1) 0.5g silicon particle (200nm) is dissolved in 10ml isopropanol, ultrasonic disperse 3h, forms solution A；
(2) it weighs 0.04g PVP, 0.4g PTFE, 4g carbon pipe to be dissolved in the deionized water of 20ml, ultrasonic 2h dissolves to be formed
Solution B；
(3) under agitation, solution A is added dropwise in solution B, drop speed is 0.01ml/s, is added dropwise subsequent
Continuous stirring 6h forms solution C；
(4) solution C is dried in vacuo, 900 DEG C of roasting 6h is then risen to 2 DEG C/min rate in a nitrogen atmosphere.
In the present embodiment, the first effect of lithium ion battery is 82%, specific discharge capacity 500mAh/g, and cycle performance is
It is 85% that 30 weeks conservation rates are recycled under 500mA
Embodiment 9:
The preparation of negative electrode material:
(1) 1g silicon particle (100nm) is dissolved in 20ml dehydrated alcohol, ultrasonic disperse 2h, forms solution A；
(2) weigh 0.4g F127,0.4g CMC is dissolved in the deionized water of 10ml, ultrasonic 1h dissolves to form solution B；
(3) 8g graphite is weighed, is slowly added into solution B under agitation and stirs 3h formation solution C；
(4) under agitation, solution A is poured into solution C, continues to stir 2h formation solution D；
(5) solution D is put into stir in 70 DEG C of water-baths and is evaporated, then risen in a nitrogen atmosphere with 5 DEG C/min rate
800 DEG C of roasting 4h.
The first effect of lithium ion battery is 85%, and specific discharge capacity 600mAh/g, cycle performance is to recycle 50 weeks under 500mA
Conservation rate is 85%.
Comparative example 1:
The preparation of negative electrode material:
(1) it weighs 0.4g PVP, 0.45g PTFE, be dissolved in the deionized water of 20ml, ultrasonic 2h dissolves to form solution A；
(2) 4g graphite is weighed, is slowly added into solution A under agitation and stirs 6h formation solution B；
(3) under agitation, 1g silicon particle (200nm) is slowly added in solution B, continues to stir 6h formation solution C；
(4) solution C is dried in vacuo, 900 DEG C of roasting 6h is then risen to 2 DEG C/min rate in a nitrogen atmosphere.
In the present embodiment, the scanning electron microscope (SEM) photograph of negative electrode material is shown in Fig. 7, and the first effect of lithium ion battery is 82%, and discharge specific volume
Amount is 600mAh/g, and cycle performance is that 30 weeks conservation rates are recycled under 200mA is 85%.
Comparative example 2:
The preparation of negative electrode material is with embodiment 1, the difference is that not containing surfactant in solution B.
In this comparative example, the first effect of lithium ion battery is 86%, specific discharge capacity 500mAh/g, and cycle performance is
It is 80% that 30 weeks conservation rates are recycled under 200mA.
In the description of this specification, term " first ", " second " are used for description purposes only, and should not be understood as instruction or
It implies relative importance or implicitly indicates the quantity of indicated technical characteristic.The spy of " first ", " second " is defined as a result,
Sign can explicitly or implicitly include one or more of the features.In the description of the present invention, the meaning of " plurality " is
Two or more, unless otherwise specifically defined.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (10)
1. a kind of method for preparing negative electrode material characterized by comprising
By silicon particle and dispersant, to form the first mixed liquor；
Surfactant, the first solvent and carbon source are mixed, to form the second mixed liquor；
First mixed liquor is mixed with second mixed liquor, and obtained mixture is successively dried, is roasted,
To obtain the negative electrode material.
2. the method according to claim 1, wherein the silicon particle meets at least one of the following conditions:
The mass ratio of the silicon particle and the dispersing agent is 1:20-1:5；
Based on the gross mass of the negative electrode material, the content of the silicon particle is 5wt%-30wt%；
The partial size of the silicon particle is 50 nanometers -300 nanometers.
3. the method according to claim 1, wherein described mix surfactant, the first solvent and carbon source
Include:
The surfactant is mixed with first solvent, to obtain third mixed liquor；
The carbon source is mixed with the third mixed liquor, to obtain second mixed liquor.
4. according to the method described in claim 3, it is characterized in that, forming the third mixed liquor further include:
The surfactant and binder are added jointly in first solvent, to obtain the third mixed liquor；
Optionally, the mass ratio of the surfactant, the carbon source and the binder is (0.01-0.1): 1:(0.01-
0.3)。
5. according to the method described in claim 4, it is characterized in that, the binder include carboxymethyl cellulose, polyethylene glycol,
At least one of polytetrafluoroethylene (PTFE), sodium alginate polyacrylic acid；
Optionally, the surfactant is selected from polyvinylpyrrolidone, polyethylene oxide-polypropylene oxide-polyethylene oxide
At least one of triblock copolymer and polyoxyethylene-poly-oxypropylene polyoxyethylene amphiphilic block copolymer；
Optionally, the carbon source in graphite, expanded graphite, graphene, doped graphene, carbon pipe and crystalline flake graphite extremely
It is one of few；
Optionally, the dispersing agent is selected from least one of dehydrated alcohol, isopropanol, deionized water.
6. the method according to claim 1, wherein first mixed liquor is mixed with second mixed liquor
Include:
First mixed liquor is added dropwise in second mixed liquor under agitation；
Optionally, the drop speed in second mixed liquor is added dropwise in first mixed liquor is 0.01ml/s-0.005ml/
s。
7. the method according to claim 1, wherein in the negative electrode material, at least portion of the silicon particle
Carbon shell is exceptionally coated on surface.
8. a kind of negative electrode material, which is characterized in that be prepared using the described in any item methods of claim 1-7.
9. a kind of cathode, which is characterized in that including negative electrode material according to any one of claims 8.
10. a kind of battery characterized by comprising
Cathode as claimed in claim 9；
Anode；
Diaphragm, the diaphragm setting is between the anode and the cathode.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112125310A (en) * | 2020-09-27 | 2020-12-25 | 昆山宝创新能源科技有限公司 | Silicon/carbon negative electrode active material and preparation method and application thereof |
| WO2023029889A1 (en) * | 2021-09-03 | 2023-03-09 | 贝特瑞新材料集团股份有限公司 | Negative electrode material, preparation method therefor and lithium-ion battery |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105489855A (en) * | 2015-11-25 | 2016-04-13 | 天津师范大学 | Core-shell silicon carbon composite negative electrode material for high-capacity type lithium ion battery and preparation method therefor |
| CN108336317A (en) * | 2017-12-12 | 2018-07-27 | 浙江天能能源科技股份有限公司 | A kind of Silicon-carbon composite material for lithium ion battery and preparation method thereof |
| CN108428876A (en) * | 2018-03-27 | 2018-08-21 | 东华大学 | A kind of high performance silicon/carbon nano composite anode material and preparation method thereof |
| CN108539186A (en) * | 2018-06-12 | 2018-09-14 | 陕西煤业化工技术研究院有限责任公司 | A kind of high-volume silicon-carbon negative electrode material and its preparation method and application |
| CN108682813A (en) * | 2018-05-10 | 2018-10-19 | 厦门大学 | A kind of preparation method and application of Si-C composite material |
| CN108807872A (en) * | 2018-04-25 | 2018-11-13 | 福建翔丰华新能源材料有限公司 | A kind of preparation method of the silicon-carbon cathode material of the small spherical structure of caged |
-
2019
- 2019-01-17 CN CN201910045146.0A patent/CN109786706A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105489855A (en) * | 2015-11-25 | 2016-04-13 | 天津师范大学 | Core-shell silicon carbon composite negative electrode material for high-capacity type lithium ion battery and preparation method therefor |
| CN108336317A (en) * | 2017-12-12 | 2018-07-27 | 浙江天能能源科技股份有限公司 | A kind of Silicon-carbon composite material for lithium ion battery and preparation method thereof |
| CN108428876A (en) * | 2018-03-27 | 2018-08-21 | 东华大学 | A kind of high performance silicon/carbon nano composite anode material and preparation method thereof |
| CN108807872A (en) * | 2018-04-25 | 2018-11-13 | 福建翔丰华新能源材料有限公司 | A kind of preparation method of the silicon-carbon cathode material of the small spherical structure of caged |
| CN108682813A (en) * | 2018-05-10 | 2018-10-19 | 厦门大学 | A kind of preparation method and application of Si-C composite material |
| CN108539186A (en) * | 2018-06-12 | 2018-09-14 | 陕西煤业化工技术研究院有限责任公司 | A kind of high-volume silicon-carbon negative electrode material and its preparation method and application |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112125310A (en) * | 2020-09-27 | 2020-12-25 | 昆山宝创新能源科技有限公司 | Silicon/carbon negative electrode active material and preparation method and application thereof |
| WO2023029889A1 (en) * | 2021-09-03 | 2023-03-09 | 贝特瑞新材料集团股份有限公司 | Negative electrode material, preparation method therefor and lithium-ion battery |
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