CN109301184A - Modified composite material, preparation method and the purposes in lithium ion battery of siliceous substrates material - Google Patents
Modified composite material, preparation method and the purposes in lithium ion battery of siliceous substrates material Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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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 modified composite material of siliceous substrates material, preparation method and in the purposes of lithium ion battery, the composite material includes silicon substrate kernel and the modified layer for being coated on the core surface, and the modified layer includes high molecular polymer coating film and the nanometer conductive material that is embedded in high molecular polymer coating film.On the one hand modified composite material of the invention can isolate electrolyte, hinder electrolyte in the side reaction on its surface, improve the overall performance of battery；On the other hand, due to polymer embed conductive nano dosage form at unique texture, it can improve structural stability while promoting electric conductivity, tension is absorbed by deformation, can improve silicon based anode material processing with use process in crushing, electrode dusting and peel off situations such as, reduce silica-base material, in charge and discharge process because huge volume expansion caused by electrode crush, remove situation, to stablize electrode structure, improve the cycle performance of battery core.
Description
Technical field
The invention belongs to technical field of lithium ion, are related to modified composite material, its preparation of a kind of siliceous substrates material
Method and purposes in lithium ion battery.
Background technique
Since lithium ion battery has high-energy density, high voltage and the properties such as environmental-friendly, it is widely used in just
It takes on formula power equipment (such as mobile phone, computer) and electric car.But due to by battery material, conductive additive and
The influence of binder etc., being difficult preparation at present has high reversible capacity, the lithium-ion electric of high circulation stability and high rate capability
Pond.
Negative electrode material is the extremely important component part of lithium ion battery, and the energy for directly influencing lithium ion battery is close
Degree and chemical property.The reversible capacity, cycle performance, high rate performance of lithium ion battery can be improved in excellent negative electrode material；
Otherwise it will cause the decaying of lithium ion performance, or even can not work.
Traditional graphite cathode material theoretical specific capacity is 372mAh/g, practical application material capacity is reachable > 360mAh/g,
Almost without room for improvement；In contrast, silicon has high specific discharge capacity (4200mAh/g), it is graphite negative electrodes material
10 times or more.The theoretical capacity of SiO is also in 1400mAh or more.Use high performance silica-base material as negative electrode active material
One of most promising route of battery energy density is improved as current.But silicon based electrode can be brought in charge and discharge process it is huge
Big volume expansion, causes dusting to be peeled off, and makes to lose electrical contact between active material and between its collector；In addition dusting
New SEI film is constantly formed in the process, further results in the lower cycle life of battery.
Carbon-coating cladding is paid close attention to the surface coating modification early stage of silica-base material, to improve the electrical conductance and mechanicalness of material
Energy.For example it includes: carbon pipe that CN 104112847A, which discloses a kind of silicon based anode material and its method, the silicon based anode material,
Silicon particle can be made to be fixed in carbon pipe since there is gap inside carbon pipe with the silicon nanoparticle being located inside the carbon pipe
In limited space, so that the volume expansion or contraction of silicon particle not only avoid influence activity in the limited space
Electronic transmission performance between material and collector, and the thickening phenomenon of SEI film is avoided, it is conducive to improve lithium battery capacity and property
Energy performance, however carbon pipe lacks ductility, and the tension of volume expansion generation can not be effectively absorbed in electrode charge and discharge process,
So the dusting of particle can not be prevented to delay.And carbon-coated method presence is carried out by carbon source high-temperature calcination in the prior art
The problem that energy consumption is high, production efficiency is low.
Summary of the invention
For the above-mentioned problems in the prior art, the purpose of the present invention is to provide a kind of modifications of siliceous substrates material
Composite material, preparation method and the purposes in lithium ion battery.The present invention contains Si/SiO by using lithium ion batteryxCathode
Material is modified layer cladding, improves electric conductivity while improving structural stability, to improve its chemical property, wraps
Include reversible capacity, first charge discharge efficiency and cycle life in battery use process.
In order to achieve the above object, the invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of modified composite material of siliceous substrates material, the composite material includes silicon substrate
Kernel, and be coated on the modified layer of the core surface, the modified layer include high molecular polymer coating film and are embedded in height
Nanometer conductive material in Molecularly Imprinted Polymer coating film.
The high molecular polymer of the invention coating film is the high molecular polymer coating film with caking property, the macromolecule
Polymer overmold film is embedded with nanometer conductive material, and the structure of this embedded nanometer conductive material can improve structural stability
Electric conductivity is improved simultaneously.
It is highly preferred that containing reactive group in the high molecular polymer coating film.
On the one hand the present invention can isolate electrolyte, electrolyte hindered to exist by introducing modified layer in silicon substrate core surface
The side reaction on its surface improves the overall performance of battery；On the other hand, it is negative to also solve silicon substrate to modified composite material of the invention
Pole material needs the problem of special protection when in use, since polymer has caking property and ductility, can pass through deformation
Tension is absorbed, so as to improve the feelings such as crushing, electrode dusting and peeling of the silicon based anode material in processing and use process
Condition, reduction silica-base material (such as Si and/or SiOxNegative electrode material) cause in charge and discharge process because of huge volume expansion
Electrode crush, removing situation, still be able to maintain the complete of material granule to a certain extent after Particle Breakage, reach steady
Fixed electrode structure improves the purpose of battery core cycle performance；The nanometer conductive material being embedded in can not only promote electric conductivity
Can, high molecular polymer coating film can also be cooperated to form the modified layer of unique texture, improve polymer stability difference itself and exist
Labile problem in cyclic process.
As the optimal technical scheme of modified composite material of the present invention, the gross mass with the composite material is
100wt% meter, the mass percentage of the modified layer are 0.5wt%~10wt%, for example, 0.5wt%, 1wt%, 2wt%,
2.5wt%, 3.5wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt% or 10wt% etc., preferably 1wt%~
5wt%.
Preferably, the group of the high molecular polymer coating film becomes Kynoar PVDF and its improves product, macromolecule
In binder, electronic conductance polymer or ionic conductance polymer any one or at least two combination.
Preferably, the high polymer binder is sodium carboxymethylcellulose (CMC), butadiene-styrene rubber (SBR) or sodium alginate
In any one or at least two combination.
Preferably, the electronic conductance polymer is any one in polyaniline, polythiophene or polypyrrole or at least two
The combination of kind.
Preferably, the ionic conductance polymer is polyacrylic acid (PAA), polyacrylamide (PAM), polyvinyl alcohol resin
In fiber (PAV) or polymethyl methacrylate (PMMA) any one or at least two combination.
It is highly preferred that including electronic conductance polymer and/or ion-conductance in the composition of the high molecular polymer coating film
Lead polymer.
" including electronic conductance polymer and/or ionic conductance polymer " of the present invention refers to: can be only comprising electronics electricity
Polymer is led, can also only include ionic conductance polymer, can also not only comprising electronic conductance polymer but also include ionic conductance
Polymer.
Since most of high molecular polymers have electrochemicaUy inert, lithium ion can be hindered in the insertion of surface of active material
With abjection, which becomes apparent in high magnification, can significantly affect the high rate performance of lithium-ion-power cell.This is preferably
In technical solution, coat by introducing electronic conductance polymer and can improve electric conductivity while keeping structural stability
Can, the composite material made has both good caking property and electric conductivity；Carrying out cladding by introducing ionic conductance polymer can
To improve lithium ionic mobility while keeping structural stability, the composite material made have both good caking property and from
Sub- migration performance；It carries out cladding by introducing electronic conductance polymer and ionic conductance polymer simultaneously and structure can kept steady
Electric conductivity and Ion transfer performance are improved while qualitative.
As the optimal technical scheme of modified composite material of the present invention, the composition of the high molecular polymer coating film
For high polymer binder, above-mentioned binder is the common binder of lithium ion battery, using these high polymer binders to silicon substrate
Kernel is coated, and not only can use the mechanical strength and ductility of polymer material, in silica-base material insertion/removal lithium embedded
The tension generated in absorption process when ion generates volume change is reduced fresh to be conducive to the holding of material granule pattern
The generation at interface；The negative electrode material that obtain and conventional binder (such as sodium carboxymethylcellulose or butylbenzene can also be improved
Rubber) processing performance when being mixed with cathode, above-mentioned factor collective effect improves the stability and kinetics of silica-base material
Can, it is applied to lithium ion battery, cycle performance, high rate performance, the capacity performance of product and the first effect of battery obtain big
Width improves.The preferably combination of sodium carboxymethylcellulose and butadiene-styrene rubber.
It is highly preferred that the composition of the high molecular polymer coating film are as follows: pressed by sodium carboxymethylcellulose and butadiene-styrene rubber
The combination of mass ratio 1:99~99:1, the mass ratio such as 1:99,5:95,10:90,20:80,25:75,30:70,40:60,
50:50,60:40,70:30,80:20,90:10 or 99:1 etc..Better improvement can be obtained using the combination of both substances
Cycle performance, high rate performance and product capacity play and the effect of first effect, and specific ratio depends on silica-base material surface to solvent
Affinity, those skilled in the art can optimize the cladding process of material therefor by both regulations ratio.
As the another optimal technical scheme of modified composite material of the present invention, the high molecular polymer coating film
Group becomes the combination of high polymer binder and ionic conductive polymer, the aforementioned high polymer binder cladding process the advantages of with
Outside, the addition of ionic conductive polymer is conducive to improve lithium ion conduction rate of the lithium ion at solid-electrolyte interface, mentions
The dynamic performance of high negative electrode material in the application, the combination acts synergistically improve the stability and kinetics of silica-base material
Can, it is applied to lithium ion battery, can reduce the polarization phenomena of battery, the cycle performance of battery, high rate performance, product
Capacity plays and first effect is greatly improved.The preferably combination of sodium alginate and polyacrylic acid, further preferably seaweed
Sour sodium and the polyacrylic acid combination of 1:4~4:1 in mass ratio.The mass ratio for example 1:4,1:3,1:2,1:2,2:1,3:1
Or 4:1 etc..
Preferably, the group of the high molecular polymer coating film becomes the combination of polyacrylamide and crosslinking agent, further
Preferably polyacrylamide and crosslinking agent polyethyleneimine (90~95) in mass ratio: the combination of (10~5), the mass ratio
For example 90:10,91:9,92:8,94:6 or 95:5 etc..
As the optimal technical scheme of modified composite material of the present invention, the modified layer with a thickness of 5nm~
100nm, for example, 5nm, 8nm, 10nm, 12nm, 15nm, 20nm, 25nm, 30nm, 32nm, 36nm, 40nm, 45nm, 50nm,
60nm, 70nm, 80nm, 90nm or 100nm etc., if thickness is less than 5nm, excessively thin clad has difficulties in actually preparation,
It is likely to result in the incomplete and uneven of cladding, to lose the effect of cladding；If thickness is greater than 100nm, blocked up packet
Coating will affect the mass transfer of negative electrode material in use, and the kinetics of material are reduced while increasing interface impedance
Energy.
Preferably, in terms of by the gross mass of the modified layer for 100wt%, the mass percentage of the nanometer conductive material
For 0.05wt%~5wt%, for example, 0.05wt%, 0.1wt%, 0.3wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%,
2.5wt%, 3wt%, 4wt% or 5wt% etc..If mass percentage is less than 0.05wt%, very few conductive agent may be high
Molecularly Imprinted Polymer clad is completely covered not having the effect of conducting electric current；If mass percentage is greater than 5wt%, excessively
Conductive agent on silicon based anode material surface, attachment may be decreased the coating ratio of high molecular polymer clad, lead to clad
Effect reduces.
Preferably, the nanometer conductive material include nano-graphite, active carbon nanoparticles, carbon nanotube, carbon nano-fiber or
In graphene any one or at least two combination, but be not limited to the above-mentioned nanometer conductive material enumerated, other abilities
The nanometer conductive material that domain commonly can reach same effect can also be used for the present invention.
Preferably, size of the nanometer conductive material in three dimensions be in 0.5nm~50 μm, such as 0.5nm,
2nm、5nm、10nm、20nm、50nm、100nm、300nm、500nm、1μm、5μm、10μm、15μm、20μm、25μm、30μm、35μ
M, 40 μm or 50 μm etc..If the size in three dimensions is respectively less than 0.5nm, too small nanometer conductive material may be by polyphosphazene polymer
It closes object clad and is completely covered and lead to not play conductive effect；If the size in three dimensions is all larger than 50 μm, excessive is received
Rice conductive material can not be uniformly distributed on silicon based anode material surface leads to that effective conductive network can not be formed in battery pole piece.
It is highly preferred that the carbon nanometer conductive material is the composite material that carbon nano-particle and one-dimensional carbon material are formed, institute
The mass ratio for stating carbon nano-particle and one-dimensional carbon material is (10~2): 1, the partial size of the carbon nano-particle in 0.5nm~2 μm,
The length of the one-dimensional carbon material is 10 μm~20 μm, and the diameter of one-dimensional carbon material is 10nm~20nm.This optimal technical scheme
In, the mass ratio of carbon nano-particle and one-dimensional carbon material for example 10:1,9:1,8:1,7:1,6:1,5:1,4:1,3:1 or 2:1
Deng；The partial size of the carbon nano-particle such as 0.5nm, 2nm, 5nm, 8nm, 10nm, 15nm, 20nm, 25nm, 30nm, 40nm,
50nm、60nm、70nm、85nm、100nm、150nm、200nm、300nm、500nm、750nm、1μm、1.2μm、1.5μm、1.6μ
M, 1.7 μm, 1.8 μm or 2 μm etc.；The length of the one-dimensional carbon material is, for example, 10 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm,
17 μm, 18 μm, 19 μm or 20 μm etc., the diameter of one-dimensional carbon material be, for example, 10nm, 11nm, 13nm, 15nm, 16nm, 17nm,
18.5nm or 20nm etc..This optimal technical scheme by by the carbon nano-particle of suitable dimension and one-dimensional carbon material according to specific ratio
Example is used cooperatively, and can not only guarantee that carbon nanometer conductive material was not coated completely by high molecular polymer in this way, but also can be in silicon substrate
Negative electrode material surface is uniformly distributed to form effective conductive network in battery pole piece, preferably promotes the electrochemistry of material
Energy.
Preferably, the nanometer conductive material is carbon nanotube and the composite material that graphene is formed, the composite material
In, the length of carbon nanotube is at 10 μm~20 μm, and 2000~20000, the two-dimensional slice size of graphene exists draw ratio
2500nm2~10000 μm2, the mass ratio of the carbon nanotube and graphene is (4~5): 1.This optimal technical scheme pass through by
The specific dimensions carbon nanotube of appropriate level is dispersed in the graphene surface of specific two-dimensional slice size, can protect to greatest extent
The mechanical performance of modified layer and the bond strength with kernel are promoted while demonstrate,proving polymer stabilisation in modified layer, and then are conducive to
Promote chemical property.It is highly preferred that the draw ratio of the carbon nanotube is 2000~4000.
Preferably, the partial size of the silicon substrate kernel is at 1 μm~20 μm, such as 1 μm, 2 μm, 3 μm, 4 μm, 4.5 μm, 5 μm, 6 μ
M, 8 μm, 10 μm, 12 μm, 14 μm, 15 μm, 17 μm, 18 μm or 20 μm etc..
Preferably, the composition of the silicon substrate kernel are as follows: the combination of silica-base material or silica-base material and carbon material, it is described
Silica-base material preferably includes Si or SiOxIn any one or two kinds of arbitrary proportions combination, 0 < x < 2, the carbon material is preferred
Combination including any one or two kinds in artificial graphite or natural graphite.The combination of the silica-base material and carbon material can be with
It is the Si or SiO of carbon-coating packagexMaterial etc., but it is not limited to the combination of silica-base material and carbon material, it can also be that other are siliceous
The negative electrode material of sill.
Second aspect, the present invention provide the preparation side of the modified composite material of siliceous substrates material as described in relation to the first aspect
Method the described method comprises the following steps:
(1) polymer is added in liquid solvent, dispersion obtains polymer paste, and conductive nano agent, dispersion is then added
Obtain mixed slurry；
(2) mixture of silica-base material or silica-base material and carbon material is added to mixed slurry obtained by step (1)
In, solid-liquid mixing；
(3) solvent is removed, the surface for making high molecular polymer be dispersed in silicon substrate kernel forms clad, obtains siliceous substrates
The modified composite material of material.
As the optimal technical scheme of the method for the invention, step (1) polymer be Kynoar PVDF and
Its improve product, high polymer binder, in electronic conductance polymer or ionic conductance polymer any one or at least two
Combination.
Preferably, the high polymer binder is any one in sodium carboxymethylcellulose, butadiene-styrene rubber or sodium alginate
Kind or at least two combination.
Preferably, the electronic conductance polymer is any one in polyaniline, polythiophene or polypyrrole or at least two
The combination of kind.
Preferably, the ionic conductance polymer is polyacrylic acid, polyacrylamide, polyvinyl alcohol resin fiber or poly- first
In base methyl acrylate any one or at least two combination.
Preferably, when the polymer is high polymer binder or high polymer binder and ionic conductive polymer
When combination, the liquid solvent includes water, N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) or N, N- dimethyl formyl
In amine (DMF) any one or at least two combination, above-mentioned solvent is suitable for existing battery process, it is not necessary to additional new
Equipment investment；Disperse the obtained solid content of slurry 20%~95%, such as 20%, 25%, 30%, 35%, 40%,
45%, 50%, 60%, 65%, 70%, 75%, 80%, 90% or 95% etc., good cladding can be taken into account within this range
Uniformity and preparation low energy consumption, and made an appointment admittedly containing the lower degree that is evenly coated, Gu it is lower containing more high then process energy consumption.
Preferably, step (1) described nanometer conductive material includes nano-graphite, active carbon nanoparticles, carbon nanotube or graphite
In alkene any one or at least two combination.
As the optimal technical scheme of the method for the invention, step (1) described dispersion are as follows: realized by stirring and uniformly divided
It dissipates.
Preferably, step (2) the solid-liquid mixing are as follows: uniformly mixing is realized by stirring.
Preferably, the method for step (3) the removal solvent is filtering.
Preferably, the method also includes carrying out step (4) after removing solvent: heat treatment, can be with by heat treatment
The crosslinking degree for improving clad makes it be unlikely in following process, use process dissolution dispersion again.
Preferably, the temperature of the heat treatment is 100 DEG C~250 DEG C, such as 100 DEG C, 120 DEG C, 150 DEG C, 165 DEG C, 185
DEG C, 200 DEG C, 210 DEG C, 225 DEG C, 235 DEG C or 250 DEG C etc., if temperature is lower than 100 DEG C, the solvent that the too low part of temperature combines
It not can be removed, clad structure can not be formed by reactions such as condensations between polymer, to prepare in next slurry
Dissolution/dispersion in journey and battery use process, cannot keep the form of clad；If temperature is higher than 250 DEG C, temperature is excessively high can
It can lead to the disengaging of reactive group and the destruction of polymer architecture, function, finally be unable to reach the effect of herein described technique
Fruit.
Preferably, the time of the heat treatment be greater than 1h, such as 1.5h, 2h, 3h, 4h, 5h, 6h, 8h, 10h, 12h, 15h,
After 18h, 20h for 24 hours etc..
The third aspect, the present invention provide a kind of cathode, and the cathode includes that modified composite material described in first aspect is made
For negative electrode active material.
Fourth aspect, the present invention provide a kind of lithium ion battery, and the lithium ion battery includes to bear described in the third aspect
Pole.
Compared with the prior art, the invention has the following beneficial effects:
(1) present invention is by introducing the nanometer for including high molecular polymer coating film and being embedded in silicon substrate core surface
On the one hand the modified layer of conductive material can isolate electrolyte, hinder electrolyte in the side reaction on its surface, improve the total of battery
Body performance；On the other hand, due to the polymer with caking property and ductility embed conductive nano dosage form at unique texture,
Structural stability can be improved while promoting electric conductivity, tension is absorbed by deformation, silicon based anode material can be improved and existed
Processing and crushing, electrode dusting and situations such as peel off in use process, reduce silica-base material (such as Si and/or SiOx cathode
Material) it is crushed in charge and discharge process because of electrode caused by huge volume expansion, situation is removed, to stablize electrode knot
Structure improves the cycle performance of battery core.
It (2), can by introducing electronic conductance polymer and/or ionic conductance polymer in high molecular polymer coating film
To improve electric conductivity and/or Ion transfer performance while keeping structural stability；By limiting high molecular polymer
The group of coating film becomes common high polymer binder, and the stability and dynamic performance of silica-base material can be improved.
(3) composite material of the invention is applied to lithium ion laminated battery, the cycle performance of battery, the capacity of product are sent out
It waves and first effect is greatly improved.
(4) become the group of high polymer binder and ionic conductive polymer by limiting the group of high molecular polymer coating film
It closes, the stability and dynamic performance of silica-base material can be improved, be applied to lithium ion battery, can reduce the pole of battery
Change phenomenon, the cycle performance of battery, the capacity of product play and first effect is greatly improved.
Specific embodiment
In order to better understand the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solving
The present invention is released, any restriction will not be constituted to the present invention.
Embodiment 1
The present embodiment provides a kind of modified composite material of siliceous substrates material, the composite materials are as follows: SiO1.5Kernel, and
It is coated on the modified layer of the core surface, the modified layer is by high molecular polymer coating film and is embedded in high molecular polymer
Active carbon nanoparticles in coating film are constituted, the composition of the high molecular polymer coating film are as follows: CMC, SBR and polyaniline press quality
Combination than 1:4:5；
D50=5 μm of partial size~10 μm of the SiO kernel, the modified layer with a thickness of 10nm~25nm, nano active
The partial size of charcoal is 10nm~20nm；
By the gross mass of modified composite material for 100wt% in terms of, the mass percentage of the modified layer is 3wt%；
By the gross mass of modified layer for 100wt% in terms of, the mass percentages of the active carbon nanoparticles is 1wt%.
Preparation method:
(1) by CMC, SBR and dispersing polyaniline in water, keep its evenly dispersed by stirring, obtain polymer paste；
Then active carbon nanoparticles are added, keeps its evenly dispersed by stirring, obtains mixed slurry；
(2) by SiO1.5Negative electrode material is added in mixed slurry, realizes that solid-liquid uniformly mixes by stirring；
(3) solvent is removed using filtration method, is dispersed in high molecular polymer containing SiO1.5Negative electrode material surface forms cladding
Layer；
(4) crosslinking degree that clad is improved by heat treatment, is not it in following process, use process again
Dissolution dispersion, heat treatment temperature are 120 DEG C, and time 3h finally obtains modified composite material.
Using:
Negative electrode active material is used as according to the ratio mixing of 1:9 using the modified composite material and artificial graphite of the present embodiment
Matter is fabricated in the same manner as in Example 1 cathode and is further assembled into laminated lithium ion battery, is surveyed using blue electric battery
Test system measures its head effect at 25 DEG C；Its circulation capacitive energy at such a temperature is tested using 45 DEG C of insulating boxs.Its head effect
The average coulombic efficiency and circulation (1C/1C) capacity of the circle of 1C/1C charge and discharge 80 circulation at (0.1C/0.1C charge and discharge) and 45 DEG C
Conservation rate data are shown in Table 1, and comparison improves 0.5% without covering material head effect, and capacity retention ratio improves 5% after 80 circles, average coulomb
Efficiency improves 0.2%.
Embodiment 2
The present embodiment provides a kind of modified composite material of siliceous substrates material, the composite materials are as follows: SiO kernel, and packet
The modified layer of the core surface is overlayed on, the modified layer is by high molecular polymer coating film and is embedded in polymer overmold film
Graphene constitute, the composition of the high molecular polymer coating film are as follows: CMC, SBR, sodium alginate and PAA are by 1:4:1:1
Combination；
D50=10 μm of partial size~15 μm of the SiO kernel, the modified layer with a thickness of 30nm~50nm；
By the gross mass of modified composite material for 100wt% in terms of, the mass percentage of the modified layer is 5wt%；
By the gross mass of modified layer for 100wt% in terms of, the mass percentage of the graphene is 1.5wt%.
Preparation method:
(1) CMC, SBR, sodium alginate and PAA are dispersed in water, it is evenly dispersed by stirring realization, obtain polymer
Slurry；
Then graphene slurry is added, it is evenly dispersed by stirring realization, obtain mixed slurry；
(2) SiO negative materials are added in slurry, realize that solid-liquid uniformly mixes by stirring；
(3) solvent is removed using evaporation, makes high molecular polymer and graphene dispersion on surface containing SiO negative materials
Form clad；
(4) crosslinking degree that clad is improved by heat treatment, is not it in following process, use process again
Dissolution dispersion, heat treatment temperature are 80 DEG C, and time 12h finally obtains modified composite material.
Using:
Negative electrode active material is used as according to the ratio mixing of 1:9 using the modified composite material and artificial graphite of the present embodiment
Matter is fabricated in the same manner as in Example 1 cathode and is further assembled into lithium ion battery, and use is same as Example 1
Method detected, head effect, average coulombic efficiency and 80 circle circulation volume conservation rate data are shown in Table 1, head effect comparison nothing
Covering material improves 0.7%, and capacity retention ratio improves 6.3% after 80 circles, and average coulombic efficiency improves 0.5%.
Embodiment 3
The present embodiment provides a kind of modified composite material of siliceous substrates material, the composite materials are as follows: the SiO of carbon-coating cladding
Kernel, and it is coated on the modified layer of the core surface, the modified layer is by high molecular polymer coating film and is embedded in high score
Carbon nanotube in sub- polymer overmold film is constituted, the composition of the high molecular polymer coating film are as follows: sodium alginate and poly- third
The olefin(e) acid combination of 1:1 in mass ratio；
D50=1 μm of partial size~6 μm of the SiO kernel of carbon-coating cladding, the modified layer with a thickness of 5nm~20nm,
The length of carbon nanotube is 10 μm -20 μm, and draw ratio is 10000~20000；
By the gross mass of modified composite material for 100wt% in terms of, the mass percentage of the modified layer is 8wt%；
By the gross mass of modified layer for 100wt% in terms of, the mass percentage of the carbon nanotube is 0.5wt%.
Preparation method:
(1) polymer is dispersed in water, it is evenly dispersed by stirring realization, obtain polymer paste；
Then carbon nanotube is added, it is evenly dispersed by stirring realization, obtain mixed slurry；
(2) SiO negative materials are added in slurry, realize that solid-liquid uniformly mixes by stirring；
(3) solvent is removed using filtration method, so that high molecular polymer is dispersed in surface containing SiO negative materials and forms cladding
Layer；
(4) crosslinking degree that clad is improved by heat treatment, is not it in following process, use process again
Dissolution dispersion, heat treatment temperature are 120 DEG C, and time 6h finally obtains modified composite material.
Using:
Negative electrode active material is used as according to the ratio mixing of 1:9 using the modified composite material and artificial graphite of the present embodiment
Matter is fabricated in the same manner as in Example 1 cathode and is further assembled into lithium ion laminated battery, using with embodiment 1
Identical method is detected, and head effect, average coulombic efficiency and 80 circle circulation volume conservation rate data are shown in Table 1, head effect pair
1.0% is improved than no covering material, capacity retention ratio improves 8.1% after 80 circles, and average coulombic efficiency improves 0.3%.
Embodiment 4
The present embodiment provides a kind of modified composite material of siliceous substrates material, the composite materials are as follows: SiO kernel, and packet
The modified layer of the core surface is overlayed on, the modified layer is by high molecular polymer coating film and is embedded in high molecular polymer packet
Conductive nano agent in overlay film, the composition of the high molecular polymer coating film are as follows: polyacrylamide (PAM) and the poly- second of crosslinking agent
Alkene imines (PEI) combination of 95:5 in mass ratio；
D50=3 μm of partial size~8 μm of the SiO kernel, the modified layer are 5nm~20nm, and the conductive nano agent is
The composite material (abbreviation Graphene/carbon nanotube composite material) that carbon nanotube and graphene are formed, in the composite material, carbon
The length of nanotube is at 10 μm~20 μm, and draw ratio is 2000~4000, and the two-dimensional slice size of graphene is in 2500nm2~
10000nm2, the mass ratio of the carbon nanotube and graphene is 4:1~5:1；
By the gross mass of modified composite material for 100wt% in terms of, the mass percentage of the modified layer is 7wt%；
By the gross mass of modified layer for 100wt% in terms of, the mass percentage of the nano-graphite is 0.5wt%.
Preparation method:
(1) it disperses polymer in water, it is evenly dispersed by stirring realization, obtain polymer paste；
Then conductive nano agent is added, it is evenly dispersed by stirring realization, obtain mixed slurry；
(2) SiO negative materials are added in mixed slurry, realize that solid-liquid uniformly mixes by stirring；
(3) solvent is removed using evaporation, is dispersed in high molecular polymer and Graphene/carbon nanotube composite material
Surface containing SiO negative materials forms clad；
(4) crosslinking degree that clad is improved by heat treatment, is not it in following process, use process again
Dissolution dispersion, heat treatment temperature are 100 DEG C, and time 3.5h finally obtains modified composite material.
Using:
Negative electrode active material is used as according to the ratio mixing of 1:9 using the modified composite material and artificial graphite of the present embodiment
Matter is fabricated in the same manner as in Example 1 cathode and is further assembled into lithium ion battery, and use is same as Example 1
Method detected, head effect, average coulombic efficiency and 80 circle circulation volume conservation rate data are shown in Table 1, head effect comparison nothing
Covering material improves 1.6%, and capacity retention ratio improves 9.3% after 80 circles, and average coulombic efficiency improves 0.6%.
Embodiment 5
The present embodiment provides a kind of modified composite material of siliceous substrates material, the composite materials are as follows: the SiO of carbon-coating cladding
Kernel, and it is coated on the modified layer of the core surface, the modified layer is by high molecular polymer coating film and is embedded in high score
Nanometer conductive material in sub- polymer overmold film is constituted, the composition of the high molecular polymer coating film are as follows: polyacrylamide
With polyethyleneimine 90:10 in mass ratio；
D50=4 μm of partial size~5 μm of the SiO kernel of carbon-coating cladding, the modified layer with a thickness of 60nm~
100nm, the nanometer conductive material are composite material (the abbreviation nano-graphite/nanometer that nano-graphite and carbon nano-fiber are formed
Carbon fibre composite), in the composite material, the partial size of nano-graphite is 20nm, and the length of carbon nano-fiber is 12 μm, is received
The diameter of rice carbon fiber is 15nm, and the mass ratio of nano-graphite and carbon nano-fiber is 5:1；
By the gross mass of modified composite material for 100wt% in terms of, the mass percentage of the modified layer is 4wt%；
By the gross mass of modified layer for 100wt% in terms of, the quality percentage of the nano-graphite/Carbon Nanofibers/Epoxy Resin Composite Materials
Content is 3.5wt%.
Preparation method:
(1) polymer is dispersed in water, it is evenly dispersed by stirring realization, obtain polymer paste；
Then conductive nano agent is added, it is evenly dispersed by stirring realization, obtain mixed slurry；
(2) SiO negative materials are added in slurry, realize that solid-liquid uniformly mixes by stirring；
(3) solvent is removed using filtration method, makes high molecular polymer and nano-graphite/Carbon Nanofibers/Epoxy Resin Composite Materials point
It is dispersed in surface containing SiO negative materials and forms clad；
(4) crosslinking degree that clad is improved by heat treatment, is not it in following process, use process again
Dissolution dispersion, heat treatment temperature are 110 DEG C, and time 4h finally obtains modified composite material.
Using:
Negative electrode active material is used as according to the ratio mixing of 1:9 using the modified composite material and artificial graphite of the present embodiment
Matter is fabricated in the same manner as in Example 1 cathode and is further assembled into lithium ion laminated battery, using with embodiment 1
Identical method is detected, and head effect, average coulombic efficiency and 80 circle circulation volume conservation rate data are shown in Table 1, head effect pair
2% is improved than no covering material, capacity retention ratio improves 10.6% after 80 circles, and average coulombic efficiency improves 0.6%.
Table 1
| First charge discharge efficiency (%) | Average coulombic efficiencies (%) | Capacity retention ratio (%) | |
| Embodiment 1 | 89.7 | 99.4 | 92.2 |
| Embodiment 2 | 89.9 | 99.7 | 93.5 |
| Embodiment 3 | 90.2 | 99.5 | 95.3 |
| Embodiment 4 | 90.8 | 99.8 | 96.5 |
| Embodiment 5 | 91.2 | 99.8 | 97.8 |
Lithium ion laminated battery obtained by various embodiments of the present invention not only has excellent cycle performance, and the capacity of product plays
It is also greatly improved with head effect.
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 modified composite material of siliceous substrates material, which is characterized in that the composite material includes silicon substrate kernel and cladding
In the modified layer of the core surface, the modified layer includes high molecular polymer coating film and is embedded in high molecular polymer packet
Nanometer conductive material in overlay film.
2. modified composite material according to claim 1, which is characterized in that the gross mass with the composite material is
100wt% meter, the mass percentage of the modified layer are 0.5wt%~10wt%, preferably 1wt%~5wt%.
3. modified composite material according to claim 1 or 2, which is characterized in that the high molecular polymer coating film
Group becomes Kynoar PVDF and its improves in product, high polymer binder, electronic conductance polymer or ionic conductance polymer
Any one or at least two combination；
Preferably, the high polymer binder be sodium carboxymethylcellulose, butadiene-styrene rubber or sodium alginate in any one or
At least two combination；
Preferably, the electronic conductance polymer is any one in polyaniline, polythiophene or polypyrrole or at least two
Combination；
Preferably, the ionic conductance polymer is polyacrylic acid and its derivative, polyacrylamide, polyvinyl alcohol resin fiber
In polymethyl methacrylate any one or at least two combination；
Preferably, it polymerize in the composition of the high molecular polymer coating film comprising electronic conductance polymer and/or ionic conductance
Object.
4. modified composite material according to claim 1-3, which is characterized in that the high molecular polymer cladding
The group of film becomes high polymer binder, the preferably combination of sodium carboxymethylcellulose and butadiene-styrene rubber, further preferably carboxylic first
Base sodium cellulosate and the butadiene-styrene rubber combination of 1:99~99:1 in mass ratio；
Preferably, the group of the high molecular polymer coating film becomes the combination of high polymer binder and ionic conductive polymer,
The preferably combination of sodium alginate and polyacrylic acid, further preferably sodium alginate and polyacrylic acid 1:4~4:1 in mass ratio
Combination；
Preferably, the group of the high molecular polymer coating film becomes the combination of polyacrylamide and crosslinking agent, further preferably
For polyacrylamide and crosslinking agent polyethyleneimine (90~95) in mass ratio: the combination of (10~5).
5. modified composite material according to claim 1-4, which is characterized in that the modified layer with a thickness of
5nm~100nm；
Preferably, in terms of by the gross mass of the modified layer for 100wt%, the mass percentage of the nanometer conductive material is
0.05wt%~5wt%；
Preferably, the nanometer conductive material includes nano-graphite, active carbon nanoparticles, carbon nanotube, carbon nano-fiber or graphite
In alkene any one or at least two combination；
Preferably, size of the nanometer conductive material in three dimensions is in 0.5nm~50 μm；
Preferably, the nanometer conductive material is the composite material that carbon nano-particle and one-dimensional carbon material are formed, the carbon nanometer
The mass ratio of particle and one-dimensional carbon material is (10~2): 1, the partial size of the carbon nano-particle is described one-dimensional in 0.5nm~2 μm
The length of carbon material is 10 μm~20 μm, and the diameter of one-dimensional carbon material is 10nm~20nm；
Preferably, the carbon nano-particle is nano-graphite and/or active carbon nanoparticles, and the one-dimensional carbon material is preferably carbon nanometer
Pipe and/or carbon nano-fiber；
Preferably, the nanometer conductive material is the composite material that carbon nanotube and graphene are formed, in the composite material, carbon
The length of nanotube is at 10 μm~20 μm, and draw ratio is 2000~20000, and the two-dimensional slice size of graphene is in 2500nm2~
10000nm2, the mass ratio of the carbon nanotube and graphene is (4~5): 1；
Preferably, the partial size of the silicon substrate kernel is at 1 μm~20 μm；
Preferably, the composition of the silicon substrate kernel are as follows: the combination of silica-base material or silica-base material and carbon material, the silicon substrate
Material preferably includes Si or SiOxIn any one or two kinds of arbitrary proportions combination, 0 < x < 2, the carbon material preferably includes
The combination of any one or two kinds in artificial graphite or natural graphite.
6. the preparation method of the modified composite material of siliceous substrates material as described in claim any one of 1-5, which is characterized in that institute
State method the following steps are included:
(1) polymer is added in liquid solvent, dispersion obtains polymer paste, and conductive nano agent is then added, and dispersion obtains
Mixed slurry；
(2) mixture of silica-base material or silica-base material and carbon material is added in mixed slurry obtained by step (1), Gu
Liquid mixing；
(3) solvent is removed, the surface for making high molecular polymer be dispersed in silicon substrate kernel forms clad, obtains siliceous substrates material
Modified composite material.
7. according to the method described in claim 6, it is characterized in that, step (1) polymer be Kynoar PVDF and
Its improve product, high polymer binder, in electronic conductance polymer or ionic conductance polymer any one or at least two
Combination；
Preferably, the high polymer binder be sodium carboxymethylcellulose, butadiene-styrene rubber or sodium alginate in any one or
At least two combination；
Preferably, the electronic conductance polymer is any one in polyaniline, polythiophene or polypyrrole or at least two
Combination；
Preferably, the ionic conductance polymer is polyacrylic acid and its derivative, polyacrylamide, polyvinyl alcohol resin fiber
In polymethyl methacrylate any one or at least two combination；
Preferably, when the combination that the polymer is high polymer binder or high polymer binder and ionic conductive polymer
When, the liquid solvent include in water, N-Methyl pyrrolidone, dimethyl sulfoxide or n,N-Dimethylformamide any one or
At least two combination, the solid content of the slurry dispersed is 20%~95%；
Preferably, step (1) described nanometer conductive material includes nano-graphite, active carbon nanoparticles, in carbon nanotube or graphene
Any one or at least two combination.
8. method according to claim 6 or 7, which is characterized in that step (1) described dispersion are as follows: realized by stirring equal
Even dispersion；
Preferably, step (2) the solid-liquid mixing are as follows: uniformly mixing is realized by stirring；
Preferably, the method for step (3) the removal solvent is filtering；
Preferably, the method also includes carrying out step (4) after removing solvent: heat treatment；
Preferably, the temperature of the heat treatment is 100 DEG C~250 DEG C；
Preferably, the time of the heat treatment is greater than 1h.
9. a kind of cathode, which is characterized in that the cathode includes the described in any item modified composite material conducts of claim 1-5
Negative electrode active material.
10. a kind of lithium ion battery, which is characterized in that the lithium ion battery includes cathode as claimed in claim 9.
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