CN106129372A - A kind of lithium ion battery negative material and preparation method thereof - Google Patents
A kind of lithium ion battery negative material and preparation method thereof Download PDFInfo
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- CN106129372A CN106129372A CN201610729465.XA CN201610729465A CN106129372A CN 106129372 A CN106129372 A CN 106129372A CN 201610729465 A CN201610729465 A CN 201610729465A CN 106129372 A CN106129372 A CN 106129372A
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 lithium ion battery, it is made up of shell core two parts, described core includes the first material with carbon element, described shell includes the second material with carbon element, described first material with carbon element is material with carbon element A and/or surface is embedded with the material with carbon element A of nano-silicon, described second material with carbon element is the material with carbon element B containing nano oxidized sub-silicon, and material with carbon element total amount accounts for 10% the 99% of described negative material quality.The invention also discloses a kind of preparation method of lithium ion battery, silica-base material is combined closely with material with carbon element by it by Electrostatic Absorption mode, simple to operate easily-controllable.
Description
Technical field
The present invention relates to lithium ion battery negative material, particularly to a kind of lithium ion battery negative with nucleocapsid structure
Material and preparation method thereof.
Background technology
Lithium ion battery based on " rocking chair " principle is because its energy density is high, running voltage is high, security performance is good, when storing
Between the advantage such as long, operating temperature range width, environmental friendliness, be not only the main powering device of current portable type electronic product, also
It is used widely in fields such as power industry, space flight and aviation and weaponrys, becomes most important secondary chemical sources of electric energy.So
And, the theoretical specific capacity of the graphite cathode material commonly used in lithium ion battery at present is only 372mAh/g, it is difficult to meet
The demand the highest to battery energy density.
In the negative material of exploitation, the theoretical specific capacity of silicon, up to 4400mAh/g, is to substitute now for energy density
There is the ideal chose of carbon negative pole material.But silicon is during removal lithium embedded, it may occur that volumetric expansion (the graphite material more than 300%
Material only has about 10%), this exacerbates the efflorescence of negative material in cyclic process and can come off from collector, thus causes electricity
, even there is the phenomenon of " dead " suddenly in the drastically decline of pond performance.And the oxygen declined relative to pure silicon material specific capacity
Changing sub-silicon materials, its bulk effect wants less, therefore better performances, but the most inefficient, and aoxidizes sub-silicon materials and exist
The change in volume of 200% is still had more than during circulating battery, therefore to suppression bulk effect and raising electrical conductivity, it is necessary to
Silica-base material is combined with carbon.
For the defect of silica-base material, the most common improvement means are will to be combined with material with carbon element after material nano again.
So on the one hand, the defect of silica-base material bulk effect can be alleviated, on the one hand can also improve the electrical conductivity of material.But it is right
The method constructed and realize combining between material in composite structure determines the final performance of material, the most silica-based
Between material and material with carbon element, combination and tightness degree are the key factors obtaining high-performance negative material.In existing preparation
In technique, generally nano silica-base material is disperseed in the liquid phase with micron material with carbon element, will be received by the difference of bi-material granularity
Rice Material cladding on the carbon material, add in addition organic carbon source as carbon coated presoma while, strengthen further both
Between adhesion.But on the one hand adopt and the joint efficiency of bi-material can be made in this way relatively low, the most substantial amounts of nanometer
Grain cannot be combined at carbon material surface but mutually reunite, and on the other hand the adhesion between bi-material is the most weak, in reality
Silica-base material is caused to be easier to come off from carbon material surface during use.
As the patent of Application No. 201210303878.3 discloses kind ball Si-C composite material and a preparation side thereof
Method, silica flour, the sub-silica flour of oxidation and dispersant wet ball grinding are obtained slurry, add graphite and conductive agent is spray-dried by it
Afterwards by pitch-coating, last carbonization obtains product.Using the Si-C composite material that the method prepares, its cycle performance has had necessarily
Improvement, but silica-base material granule is only mounted on graphite composite powder by physics, can not be in close contact with graphite, storehouse first
Human relations efficiency is relatively low.And for example the patent of Application No. 201310511216.X discloses a kind of silicon/silicon monoxide/carbon/titanium dioxide
The composite of silicon/carbon multiplet.The method by coated silica after silicon, the sub-silicon of oxidation and carbonization of sucrose,
Again mix with polrvinyl chloride and carry out ball milling and secondary carbonization cladding.The method introduces inactive silicon dioxide, silicon substrate
Expect with carbon between structure construct the most relatively simple so that the bulk effect of silica-base material fails to obtain bigger buffering, follows
Ring poor-performing.The most repeatedly ball milling the most easily makes silicon materials be exposed to product surface directly to contact with electrolyte.
Summary of the invention
It is an object of the invention to provide a kind of lithium ion battery negative material and preparation method thereof, to solve existing negative pole
The technological deficiency that material coulombic efficiency first is low, cycle performance of battery is poor.
In order to realize foregoing invention purpose, technical scheme is as follows:
A kind of lithium ion battery negative material, generally nucleocapsid structure, described shell is coated on the outer surface of described core, described
Core is spherical or class is spherical, and described core includes that the first material with carbon element, described shell include that the second material with carbon element, described first material with carbon element are carbon
Materials A and/or surface are embedded with the material with carbon element A of nano-silicon, and described second material with carbon element is the material with carbon element B containing nano oxidized sub-silicon,
Material with carbon element total amount accounts for the 10%-99% of described negative material quality；
Wherein, described material with carbon element A is selected from porous graphite, expanded graphite, pore-creating graphite, native graphite, Delanium, centre
One or more in phase carbosphere, soft carbon and hard carbon, the specific surface area of described carbonaceous mesophase spherules, soft carbon and hard carbon is equal
For 2-200m2/g；Described material with carbon element B is organic cracking carbon, and described nano oxidized sub-silicon is surface receiving through modification
The sub-silicon grain of rice oxidation, described nano oxidized sub-silicon is combined with described first material with carbon element by Electrostatic Absorption mode.
In above-mentioned negative material, there is substantial amounts of class aromatic ring structure in graphite-like carbon material surface, thus forms the big π of delocalization
Key, when pH value is more than its isoelectric point, IP, its surface can present elecrtonegativity, additionally, have the carbon material surface of certain specific surface area
Can adsorb-COOH and-OH group, rear surface of dissociating in aqueous solvent also can present elecrtonegativity.And nano silica-base material (bag
Including nano-silicon, nano oxidized sub-silicon etc.) specific surface area is big, and particle surface is prone to the OH in adsorbent solution-And H+Ion, so that
Its surface has an abundant hydroxyl functional group, and grafted amino group-NH on these avtive spots2After, dissociate in aqueous solution
After become-NH+, can be so electropositive by based nanoparticle surface conversion.Therefore, by nano silica-base material and graphite-like
When the material with carbon element of material with carbon element or certain specific surface area combines under certain condition, by quiet between xenogenesis charge material in solution
It is electrically coupled power, it is possible to silica-base material is combined closely with material with carbon element, thus ensure that silica-based while suppression bulk effect
Material and material with carbon element have good electrical contact during circulating battery so that above-mentioned negative material first charge-discharge efficiency
Height, Volumetric expansion are low, and cycle performance is excellent.
And, the preparation method of a kind of lithium ion battery negative material, can be used for preparing above-mentioned negative material, it include with
Lower step:
Prepare above-mentioned first material with carbon element, as above-mentioned core；
By the modifying surface of nano oxidized sub-silicon grain is processed, by nano oxidized sub-silicon by Electrostatic Absorption side
Formula is combined with described first material with carbon element, it is thus achieved that the first material；
The presoma of described first material with above-mentioned material with carbon element B is combined, it is thus achieved that the second material；
Described second material is carried out high-temperature process in an inert atmosphere, obtains described negative material.
Above-mentioned preparation method uses above-mentioned first material with carbon element, because material with carbon element therein can produce negative electricity under certain condition
Property (reason is as above), then be allowed to positively charged by the modifying surface of nano oxidized sub-silicon grain is processed, the most positive and negative
Electrically attract each other, achieve combining closely of silica-base material and material with carbon element by electrostatical binding power so that silica-base material makes
It is not easy in to come off from carbon material surface, it is suppressed that silica-base material bulk effect in circulating battery, and has good
Electrical contact.And the method is simple to operate, condition is easily-controllable, is readily available negative material of good performance.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 is the structure chart of the lithium ion battery negative material that embodiment 1 prepares；
Fig. 2 is the structure chart of the lithium ion battery negative material that embodiment 2 prepares；
Fig. 3 is the structure chart of the lithium ion battery negative material that embodiment 3 prepares；
Fig. 4 is the SEM photograph of the negative material of the embodiment of the present invention 1；
Fig. 5 is the first charge-discharge curve of the negative material of the embodiment of the present invention 1；
Fig. 6 is the cycle performance curve of the negative material of the embodiment of the present invention 1；
Wherein 1 is material with carbon element A, and 2 is nano-silicon, and 3 is nano oxidized sub-silicon, and 4 is material with carbon element B, and 5 is material with carbon element C.
Detailed description of the invention
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, below in conjunction with
Embodiment and accompanying drawing, be further elaborated to the present invention.Should be appreciated that specific embodiment described herein is only used
To explain the present invention, it is not intended to limit the present invention.Say the most merely " material with carbon element A " and " material with carbon element B " refer to the most siliceous or
The material with carbon element of other materials, if containing silicon or other materials, can clearly modify before at " material with carbon element A " and " material with carbon element B "
Illustrating, such as surface is embedded with the material with carbon element A of nano-silicon, refers to be embedded with nano-silicon on material with carbon element A, and other are in like manner.
The embodiment of the present invention provides a kind of lithium ion battery negative material, generally nucleocapsid structure, and described shell is coated on institute
Stating the outer surface of core, described core is spherical or class is spherical, and described core includes that the first material with carbon element, described shell include the second material with carbon element,
Described first material with carbon element is material with carbon element A and/or surface is embedded with the material with carbon element A of nano-silicon, and described second material with carbon element is containing nanometer
The material with carbon element B of the sub-silicon of oxidation, material with carbon element total amount accounts for the 10%-99% of described negative material quality；
Specifically, in described core, described first material with carbon element be material with carbon element A or surface be embedded with nano-silicon material with carbon element A or
The mixture of material with carbon element A of nano-silicon " material with carbon element A and the surface are embedded with ".Material with carbon element A is graphite-like material with carbon element or has a definite proportion
The material with carbon element of surface area, for micro-selected from porous graphite, expanded graphite, pore-creating graphite, native graphite, Delanium, mesocarbon
One or more in ball, soft carbon and hard carbon, the specific surface area of described carbonaceous mesophase spherules, soft carbon and hard carbon is 2-
200m2/g.Because itself there is a large amount of class aromatic ring structure in graphite-like carbon material surface, thus forms delocalization big π key, big at pH value
When its isoelectric point, IP, its surface presents elecrtonegativity.For other material with carbon elements, there is not class as graphite-like material with carbon element in surface
Aromatic ring structure, but after deliberation, it is 2-200m in specific surface area2/ g, preferably 5-100m2Under/g, material with carbon element can provide more
Adsorption site, thus reaching graphite-like carbon material surface such as by adsorption is electronegative effect.Preferably, can be simultaneously
The specific surface area limiting graphite-like material with carbon element is 2-200m2/ g (preferably 5-100m2/ g), so, class aromatic ring structure adds specific surface
The long-pending adsorption effect provided, can make graphite-like material with carbon element elecrtonegativity higher.Why specific surface area is limited in certain
In the range of, it being because specific surface area the biggest, absorbability is the strongest, but specific surface area is crossed conference reduction covered effect thus affected head
Secondary efficiency.
In described core, material with carbon element A mass ratio in described core is preferably 10%-100%, so can provide enough
Adsorption site, improve further the combination rate of silica-base material.In " being embedded with the material with carbon element A of nano-silicon ", described nano-silicon is permissible
For graininess or film like, when for graininess, particle diameter is preferably 1-300nm, is so conducive to nano-silicon on material with carbon element A
Absorption；When for film like, thickness is preferably 0.5-300nm, so can be conducive to the performance of material overall performance.Described table
Face is embedded with the material with carbon element A of nano-silicon and can be obtained by purchase or (need to carry out nano-silicon surface by liquid phase Electrostatic Absorption
Modification) method and chemical vapour deposition technique prepare.Wherein, liquid phase Electrostatic Absorption method is optimal way, because electrostatic
Absorption changes existing silicon-carbon physics and carries form so that the combination between silicon-carbon is stronger, described core compound
Structure is more tight, and silicon materials are preferably distributed on the carbon material simultaneously.
In described shell, material with carbon element B is organic cracking carbon, is i.e. obtained by organic cracking, such as by phenolic resin, ring
One or more organic cracking in epoxy resins, glucose, fructose, sucrose, Colophonium, citric acid forms.Material with carbon element B
Mass ratio in described shell is preferably 3%-97%, and it is applied not only to cladding and bonding the first material with carbon element, it is also possible to be used for gluing
Close nano oxidized sub-silicon.Described nano oxidized sub-silicon is the surface nano oxidized sub-silicon grain through modification, its surface in
Electropositive, can by Electrostatic Absorption mode (principle and above-mentioned nano-silicon are identical with material with carbon element A Electrostatic Absorption mode) with can be in negative
Electrical described first material with carbon element combines.So by the electrostatical binding power between xenogenesis electric charge so that silica-base material and carbon material
Material is combined closely, thus ensure that silica-base material has during circulating battery with material with carbon element while suppression bulk effect
Good electrical contact, inhibits volumetric expansion while improving electrical conductivity, thus is greatly improved the effect of coulomb first of material
Rate and circulating ratio performance.The modification that described nano oxidized sub-silicon is made presents electropositive grafting change for being allowed to surface
Property, such as " nano silica-base material specific surface area is big, and particle surface is prone to the OH in adsorbent solution-And H+Ion, so that its
Surface has an abundant hydroxyl functional group, forms many avtive spots " on the basis of on surface activity site grafted amino group-
NH2, at the dissociation in water of aqueous solution, become-NH+, can be so electropositive by based nanoparticle surface conversion.Certainly,
Otherwise, it is also possible to make material with carbon element positively charged, nano silica-base material negatively charged by other method of modifying, thus realize electrostatic
Absorption combines.The nano oxidized sub-silicon of graininess has certain activity, and preferable particle size is 1-500nm, to obtain preferably activity,
Ensure the film performance of the sub-silicon of oxidation.The sub-silicon of oxidation generally by silicon and silicon dioxide at vacuum furnace high-temperature dismutation reaction
After, obtained by cooling deposition.
As improving further, it is 0-that above-mentioned shell may also include material with carbon element C, the material with carbon element C mass ratio in described shell
20%.Material with carbon element C is preferably gas cracking carbon, fine and close can be coated on the outer surface of described second material with carbon element, it is ensured that silicon materials are not
Occur directly to contact, so that the performance of negative material is more excellent with electrolyte.The integral thickness of described shell is preferably
0.1-5 μm, so can ensure that the performance of negative material excellent properties.
In above-mentioned negative material, it is preferable that when the first material with carbon element contains nano-silicon, and the second material with carbon element contains nano oxidized Asia
During silicon, it is possible to alleviate nano silica-base material bulk effect during Li insertion extraction well.Because the advantage of nano-silicon is
Its capacity is high, first effect height, but cycle performance is poor.The advantage of the sub-silicon of oxidation is good cycle, but capacity is low, and first effect is low.
Therefore compared to the sub-silicon of simple nano-silicon or oxidation, the advantage of both materials just can be complementary, energy after compound use
Enough while playing respective advantage, making up respective defect, reach capacity, first effect and the balance of cycle performance, this is inherence
Composition and the comprehensive function of formal structure.Add the cladding of material with carbon element C, it is possible to silicon is had relatively during Li insertion extraction
Short lithium ion transport distance, and inhibit volumetric expansion while improving electrical conductivity, thus it is greatly improved the head of material
Secondary coulombic efficiency and circulating ratio performance.
The embodiment of the present invention additionally provides the preparation method of a kind of lithium ion battery negative material, can be used for preparing above-mentioned bearing
Pole material, it comprises the following steps:
S01, prepare above-mentioned first material with carbon element, as above-mentioned core；
S02, by the modifying surface of nano oxidized sub-silicon grain is processed, nano oxidized sub-silicon is inhaled by electrostatic
Subsidiary formula formula is combined with described first material with carbon element, it is thus achieved that the first material；
S03, the presoma of described first material with above-mentioned material with carbon element B is combined, it is thus achieved that the second material；
S04, described second material is carried out high-temperature process in an inert atmosphere, obtain described negative material.
Specifically, in step S01, as it was previously stated, described first material with carbon element is material with carbon element A and/or surface is embedded with nanometer
The material with carbon element A of silicon, described material with carbon element A are graphite-like material with carbon element or have certain specific surface area (2-200m2/ g, preferably 5-100m2/
G) material with carbon element, be selected from porous graphite, expanded graphite, pore-creating graphite, native graphite, Delanium, carbonaceous mesophase spherules,
One or more in soft carbon and hard carbon, the specific surface area of described carbonaceous mesophase spherules, soft carbon and hard carbon is 2-
200m2/g.Described first material with carbon element by buying or can prepare.If the first material with carbon element is embedded with nano-silicon, preparation method
Can be liquid phase Electrostatic Absorption method and chemical vapour deposition technique.Concrete preparation process can be such that
Liquid phase Electrostatic Absorption method: being added in organic solvent by material with carbon element A, solid content is 5%-50%, 0.5-2 is little in stirring
Time, obtain suspending liquid A, wherein material with carbon element A surface negatively charged；Being added by nano-silicon in organic solvent, the particle diameter of nano-silicon is
1-300nm, preferably 1-70nm, solid content is 3%-50%.It is 5%-100% by the mass ratio with nano-silicon subsequently, preferably
For the ratio of 20%-70%, add organic amine or amino silicane coupling agent, and instill ammonia and/or vinegar acid for adjusting pH value extremely
4-12, preferably 5-10, in temperature 20-80 DEG C, under conditions of preferably 40-70 DEG C, logical nitrogen ultrasonic agitation 0.5-8 hour,
Being preferably 1-5 hour, obtain suspension B, wherein nano-silicon surface is positively charged.After suspending liquid A, B mixing, stir 0.5-2
Hour, it is thus achieved that combine and be dispersed in the surface in organic solution by xenogenesis charge adsorption effect and be embedded with the material with carbon element A of nano-silicon.
Wherein, stir speed (S.S.) is 500-2000rpm, described organic solvent be ethanol, ethylene glycol, isopropanol, 1,2 propylene glycol, carbitol,
One or more in toluene, normal hexane, hexamethylene, dimethylformamide, N-Methyl pyrrolidone.Described organic amine is
Ethanolamine, ethylenediamine, N, N '-diethyl triamine, N, one or more in N '-dimethyl ethylenediamine；Described amino silicone
Alkane coupling agent is 3-aminopropyl triethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxy dimethoxysilane, N-2-ammonia second
Base-3-aminopropyl trimethoxysilane, 3-aminopropyltriethoxy diethoxy silane, gamma-aminopropyl-triethoxy-silane, γ-
Aminopropyl trimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N-β-(aminoethyl)-γ-ammonia
One or more in hydroxypropyl methyl diethoxy silane.It is dispersed in organic solution by what liquid phase adsorption method prepared
The material with carbon element A being embedded with nano-silicon is suspension I.
Chemical vapour deposition technique: material with carbon element A is put in the CVD stove being connected with hydrogen, noble gas and silicon source gas, wherein
Volume ratio 1:10-30:0.1-8 of hydrogen, noble gas and silicon source gas, with the ramp of 1-5 DEG C/min to 500-900 DEG C
After, it being incubated 0.5-10 hour, prepared surface is embedded with the material with carbon element A of nano-silicon, is product I.Described silicon source gas is SiH4Or
SiHCl3Or other conventional silicon source gases, described noble gas is nitrogen or argon.
Therefore, described first material with carbon element, can be obtained by purchase or select above-mentioned suspending liquid A, suspension I, product I or
The mixture of material with carbon element A of nano-silicon " material with carbon element A and the surface are embedded with ", as nuclear material, is for further processing.
In S02 step, using the first material with carbon element (the such as product I or " material with carbon element A and surface are embedded with nano-silicon as core
The mixture of material with carbon element A ") add in organic solvent, solid content 10%-50%, stir 0.5-2 hour, obtain core suspension
I, it is also possible to choosing above-mentioned prepared suspending liquid A, suspension I directly as core suspension I, carbon material surface therein is with negative
Electrically.Adding in organic solvent by nano oxidized sub-silicon grain, the particle diameter of nano oxidized sub-silicon is 1-500nm, preferably 1-
200nm, nano oxidized sub-silicon grain solid content is 3-30%.It is 5%-100% by the mass ratio with nano oxidized sub-silicon subsequently,
It is preferably the ratio of 20%-70%, adds organic amine or amino silicane coupling agent (being used for providing amino), and instill ammonia
And/or vinegar acid for adjusting pH value (is affected the quantity in granule surface activity site to 4-12, thus improves granule by regulation pH value
Surface activity, promotes being smoothed out of graft modification), preferably 5-10, in temperature 20-80 DEG C, the condition of preferably 40-70 DEG C
Under, logical nitrogen ultrasonic agitation 0.5-8 hour, preferably 1-5 hour, obtain suspension II, nano oxidized sub-silicon face therein
With electropositive.After core suspension I, suspension II mixing, stir 0.5-2 hour, it is thus achieved that containing " by Electrostatic Absorption mode
In conjunction with, the first material being adsorbed with nano oxidized sub-silicon that is dispersed in organic solution " solution, the i.e. first material solution.
Described stir speed (S.S.) is 500-2000rpm, described organic solvent be ethanol, ethylene glycol, isopropanol, 1,2 propylene glycol, carbitol,
One or more in toluene, normal hexane, hexamethylene, dimethylformamide, N-Methyl pyrrolidone.Described organic amine is
Ethanolamine, ethylenediamine, N, N '-diethyl triamine, N, one or more in N '-dimethyl-ethylenediamine；Described amino silicone
Alkane coupling agent is 3-aminopropyl triethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxy dimethoxysilane, N-2-ammonia second
Base-3-aminopropyl trimethoxysilane, 3-aminopropyltriethoxy diethoxy silane, gamma-aminopropyl-triethoxy-silane, γ-
Aminopropyl trimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N-β-(aminoethyl)-γ-ammonia
One or more in hydroxypropyl methyl diethoxy silane.
In S03 step, the presoma of described material with carbon element B be phenolic resin, epoxy resin, glucose, fructose, sucrose,
One or more in Colophonium, citric acid.Described first material and the complex method of material with carbon element B, may is that described carbon
The presoma dispersed with stirring of material B, in organic solvent or water, obtains solution I, and wherein solid content is 1%-50%, stir speed (S.S.)
For 500-2000rpm, mixing time is 0.5-5 hour；Described organic solvent be ethanol, propanol, isopropanol, the one of oxolane
Plant or more than one.By solution I and the first material solution mix and blend, obtaining mixed solution, wherein, stir speed (S.S.) is 500-
2000rpm, mixing time is 0.5-5 hour.Described mixed solution can be spray-dried, prepare described second material.
In step S04, the condition of high-temperature process is, heating rate is set as 1-10 DEG C/minute, room temperature rise to 600-
Be incubated natural cooling after 1-8 hour after 1100 DEG C, described noble gas can select nitrogen, argon or other, pass through high temperature
Purpose product negative material is obtained after process.
After step S04, it is also possible to by chemical vapour deposition technique, gas is cracked carbon, i.e. material with carbon element C, is coated on
State on the outer surface of negative material.So while improving electrical conductivity, it is possible to be substantially reduced silica-base material direct with electrolyte
The probability of contact, so that the performance of material is the most excellent.Its concrete mode is: 3%-25% in mass ratio is by before catalyst
The product (i.e. early stage product) driving body prepared with step S04 adds to organic solvent and/or water jointly, and the solid content of solution is
5%-30%, is dried after stirring 0.5-2 hour, prepares the complex of catalyst and early stage product；Then put it into and be connected with carbon
In the CVD stove of source gas, noble gas and hydrogen, heat 0.5-10 hour in the environment of 500-1000 DEG C.Described catalyst
Presoma is: one or more in ferrum, copper, the nitrate of nickel or acetate；Described organic solvent is ethanol, isopropyl
One or more in alcohol, acetone；Described carbon-source gas is at least one in acetylene, ethylene or methane.Described inertia
Gas can be nitrogen or argon.
Above-mentioned preparation method, is modified silica-base material, uses electrostatic absorption principle, it is thus achieved that the silicon-carbon combined closely is multiple
Closing negative material, simple to operate, condition is easily-controllable, it is possible to the negative material of excellent, is suitable to batch production.
Now as a example by concrete lithium ion battery negative material and preparation method thereof, the present invention is carried out the most specifically
Bright.The identical name related in each embodiment, does not represent and must be same material or refer to, each in the most each embodiment
It is separate for planting name.In the same embodiment, identical name represents identical material or same refers to.
Embodiment 1
(1) being dispersed in isopropanol by the spherical graphite of 100g mean diameter 13 μm, the solid content of suspension is 30%, with
The speed of 1500rpm stirs 0.5 hour, prepares suspending liquid A；The silica flour of 5g mean diameter 50nm is dispersed in isopropanol, outstanding
The solid content of supernatant liquid is 20%, after adding the 3-aminopropyltriethoxy diethoxy silane of 1g, with ammonia, pH value is adjusted to 9, at nitrogen
Under gas shielded, heating in water bath is to 40 DEG C, ultrasonic agitation 3 hours, and stir speed (S.S.) is 1000rpm, prepares suspension B.By suspending liquid A,
After B mixing, prepare, after stirring 1 hour with the speed of 1500rpm, the first material with carbon element being dispersed in isopropanol, it is thus achieved that containing first
The suspension one of material with carbon element.
(2) being dispersed in isopropanol by the oxidation Asia silica flour of 20g mean diameter 150nm, the solid content of suspension is 20%,
After adding the 3-aminopropyltriethoxy diethoxy silane of 5g, with ammonia, pH value being adjusted to 8, heating in water bath is to 50 under nitrogen protection
DEG C, ultrasonic agitation 3 hours, stir speed (S.S.) is 1000rpm, prepares suspension two.
(3), after suspension one and suspension two being mixed, after stirring 2 hours with the speed of 1000rpm, solution one is obtained；Will
15g Colophonium adds in oxolane, and the solid content of Colophonium is 15%, after stirring 1 hour with the speed of 1500rpm, adds molten
Liquid one, stirs with the speed of 1500rpm and obtains complex one after within 3 hours, being spray-dried.
(4) complex one is placed in the atmosphere furnace of logical Ar, and with the heating rate of 3 DEG C/min, temperature is risen to 900
DEG C, constant temperature is down to room temperature after 5 hours naturally, carries out product pulverizing, sieving.
(5) product after sieving is carried out classification, prepare the lithium ion battery silicon-carbon composite negative pole material with nucleocapsid structure
Material.
The present embodiment prepare product structure as it is shown in figure 1, its SEM photograph as shown in Figure 4, the mean diameter of composite
About 13 μm, based nanoparticle is more uniformly covered on material surface.(Fig. 5,6) is understood, this reality via performance test
The material executing example gained has efficiency and cycle performance first.
Embodiment 2
(1) the microdilatancy spherical graphite of 100g mean diameter 14 μm is put into it is connected with SiH4、H2With in the CVD stove of Ar, SiH4
Flow be 15ml/min, H2Flow be 10ml/min, Ar flow be 200ml/min, 800 DEG C/heating 2 hours, prepare the
One material with carbon element.
(2) being disperseed in ethanol by the oxidation Asia silica flour of 30g mean diameter 150nm, the solid content of suspension is 20%, adds
After entering the ethanolamine of 5g, with ammonia, pH value being adjusted to 10, heating in water bath is to 60 DEG C under nitrogen protection, and ultrasonic agitation 4 hours is stirred
Mixing speed is 1500rpm, prepares suspension two.
(3) the first material with carbon element that step (1) prepares is put in ethanol, solid content 20%, stirs with speed 1000rpm
2 hours prepared suspensions one.After suspension one and suspension two are mixed, obtain molten after stirring 2 hours with the speed of 1000rpm
Liquid one；Being added in ethanol by 15g phenolic resin, the solid content of phenolic resin is 5%, stirs 1 hour with the speed of 1000rpm
After, add solution one, stir with the speed of 1500rpm and obtain complex one after within 5 hours, being spray-dried.
(4) complex one is placed in the atmosphere furnace of logical Ar, and with the heating rate of 5 DEG C/min, temperature is risen to 950
DEG C, constant temperature is down to room temperature after 3 hours naturally, carries out product pulverizing, sieving.
(5) product after sieving is carried out classification, prepare the lithium ion battery silicon-carbon composite negative pole material with nucleocapsid structure
Material.
The product structure that the present embodiment prepares is as in figure 2 it is shown, have efficiency and cycle performance first.
Embodiment 3
(1) being disperseed in ethanol by the carbonaceous mesophase spherules of 100g mean diameter 12 μm, the solid content of suspension is 25%,
Stir 1 hour with the speed of 1500rpm, prepare suspending liquid A；The silica flour of 3g mean diameter 50nm is dispersed in normal hexane, outstanding
The solid content of supernatant liquid is 15%, after the N, N ' of addition 1g-diethylenetriamines, with acetum, pH value is adjusted to 5, protects at nitrogen
Protecting lower heating in water bath to 70 DEG C, ultrasonic agitation 3 hours, stir speed (S.S.) is 1000rpm, prepares suspension B.By suspending liquid A, B mixes
After conjunction, prepare dispersion the first material with carbon element in organic solvent with the speed of 1500rpm after stirring 1 hour, it is thus achieved that containing first
The suspension one of material with carbon element.
(2) being dispersed in normal hexane by the oxidation Asia silica flour of 30g mean diameter 200nm, the solid content of suspension is 20%,
After the N, N ' of addition 10g-diethylenetriamines, with ammonia, pH value being adjusted to 8, heating in water bath is to 70 DEG C under nitrogen protection, super
Sound stirs 3 hours, and stir speed (S.S.) is 1000rpm, prepares suspension two.
(3), after suspension one and suspension two being mixed, after stirring 2 hours with the speed of 1000rpm, solution one is obtained；Will
20g citric acid adds in 100ml ethanol, after stirring 0.5 hour with the speed of 1000rpm, adds solution one, with 1500rpm
Speed stirring within 1 hour, be spray-dried after obtain composite I.
(4) complex one is placed in the atmosphere furnace of logical Ar, and with the heating rate of 3 DEG C/min, temperature is risen to 900
DEG C, constant temperature is down to room temperature after 4 hours naturally, carries out product pulverizing, sieving.
(5) being added in ethanol with 100g step (4) product by 8g cobalt nitrate, the solid content of solution is 20%, with 1000rpm
Speed stir 2 hours be dried, then desciccate is put into and is passed through C2H2、H2With in the CVD stove of Ar, little at 800 DEG C of constant temperature 3
Time.
(6) product is sieved, classification, prepare and there is the silicon-carbon composite cathode material of lithium ion battery of nucleocapsid structure.
The product structure that the present embodiment prepares is as shown in Figure 3.
Embodiment 4
According to condition and the step operation of embodiment 1, difference is: the people that material with carbon element A is mean diameter 12 μm of use
Making graphite, amino grafting molecules is 3-aminopropyl triethoxysilane, and the mass ratio of graphite, silicon and oxidation Asia silicon is 100:2:
40, in step (3), before spray drying, use sucrose is organic carbon source, and solvent is water.Spray drying after-baking temperature
Degree is 950 DEG C, and roasting time is 3 hours.
Embodiment 5
According to condition and the step operation of embodiment 2, difference is: the material with carbon element A of use is the soft of mean diameter 10 μm
Material with carbon element, adds 1.5 hours at 600 DEG C of constant temperature and carries out CVD deposition silicon, and the amino grafting molecules of use is ethylenediamine, graphite and oxygen
The mass ratio changing sub-silicon is 100:30.In step (3), before spray drying, use Colophonium is organic carbon source, is spray-dried
After-baking temperature is 900 DEG C, and roasting time is 3 hours.
Embodiment 6
(1) being disperseed in ethanol by the oxidation Asia silica flour of 40g mean diameter 130nm, the solid content of suspension is 20%, adds
After entering the N-2-aminoethyl-3-aminopropyl trimethoxysilane of 20g, with ammonia, pH value being adjusted to 9, water-bath adds under nitrogen protection
Heat is to 55 DEG C, and ultrasonic agitation 4 hours, stir speed (S.S.) is 1500rpm, prepares suspension one.
(2), during the microdilatancy spherical graphite of 100g mean diameter 15 μm adds suspension one, stir with the speed of 1000rpm
Solution one is obtained after 2 hours；15g Colophonium is added in oxolane, after stirring 1 hour with the speed of 1500rpm, add molten
Liquid one, stirs with the speed of 1500rpm and obtains complex one after within 6 hours, being spray-dried.
(4) complex one is placed in the atmosphere furnace of logical Ar, and with the heating rate of 5 DEG C/min, temperature is risen to 900
DEG C, constant temperature is down to room temperature after 6 hours naturally, carries out product pulverizing, sieving.
(5) product after sieving is carried out classification, prepare that to have the lithium ion battery silicon cathode material of nucleocapsid structure (silica-based
Material only has the oxidation Asia silicon in shell).
Following comparative example be do not use Electrostatic Absorption mode combine obtained by the preparation method of silicon-carbon composite cathode material:
Comparative example 1
Comparative example 1, and the spherical graphite of 100g mean diameter 13 μm, the silica flour of 5g mean diameter 50nm and 25g is flat
All oxidation Asia silica flours of particle diameter 150nm are dispersed in isopropanol, solid content 20%, stir 1 hour with the speed of 1500rpm,
To suspension one.Being added in oxolane by 15g Colophonium, the solid content of Colophonium is 15%, stirs 1 with the speed of 1500rpm little
Shi Hou, adds to suspension one, stirs with the speed of 1500rpm and obtains complex one after within 3 hours, being spray-dried.Will be multiple
Compound one is placed in the atmosphere furnace of logical Ar, and with the heating rate of 3 DEG C/min, temperature rises to 900 DEG C, constant temperature after 3 hours from
So it is down to room temperature, carries out product pulverizing, sieving.Prepare containing silicon, the silicon-carbon composite cathode material of the sub-silicon of oxidation.
Comparative example 2
Comparative example 6, by the microdilatancy spherical graphite of 100g mean diameter 15 μm, the oxidation of 40g mean diameter 130nm
Sub-silica flour disperses in ethanol, solid content 20%, stirs 1 hour with the speed of 1500rpm, obtains suspension one.By 15g Colophonium
Adding in oxolane, the solid content of Colophonium is 15%, after stirring 1 hour with the speed of 1000rpm, adds to suspension one
In, stir with the speed of 1500rpm and obtain complex one after within 6 hours, being spray-dried.Complex one is placed in the gas of logical Ar
In atmosphere stove, and with the heating rate of 5 DEG C/min, temperature rising to 900 DEG C, constant temperature was down to room temperature, naturally by product after 6 hours
Carry out pulverizing, sieving.Prepare the silicon-carbon composite cathode material containing the sub-silicon of oxidation.
Performance test methods:
The chemical property of employing following methods test material: the sample of Example synthesis respectively, with binding agent PAA
Glue, conductive agent Super-P mix according to the weight ratio of 80:1:1, add appropriate deionized water as dispersant furnishing slurry,
It is coated on Copper Foil, and vacuum dried, roll-in, punching, it being prepared as pole piece, electrode is used metal lithium sheet, electrolyte uses
1mol/L LiPF6EC:DMC:EMC solution (volume ratio 1:1:1), barrier film use microporous polypropylene membrane, at the hands of full argon
After casing is assembled into CR2016 button cell, at room temperature use the electric discharge of electric current density constant current constant voltage and the constant current of 60mA/g
Charge mode is circulated performance test, and charging/discharging voltage interval is 0.01-1.5V, and test equipment uses Shenzhen's new Weir electricity
Sub-company limited BTS-400 battery test system.
After tested, the negative material correlated performance test result that prepared by above-described embodiment 1 to embodiment 6 and comparative example 1-2
The most as shown in table 1.
The chemical property after battery made by the material of each embodiment of table 1.
As can be seen from the table above, in the embodiment using Electrostatic Absorption method, obtained negative material performance table
Now good, the especially cycle performance of material is significantly increased compared with comparative example.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention
Any amendment, equivalent and the improvement etc. made within god and principle, should be included within the scope of the present invention.
Claims (11)
1. a lithium ion battery negative material, generally nucleocapsid structure, described shell is coated on the outer surface of described core, described core
For spherical or class is spherical, it is characterised in that described core includes that the first material with carbon element, described shell include the second material with carbon element, described first
Material with carbon element is material with carbon element A and/or surface is embedded with the material with carbon element A of nano-silicon, and described second material with carbon element is containing nano oxidized sub-silicon
Material with carbon element B, material with carbon element total amount accounts for the 10%-99% of described negative material quality；
Wherein, described material with carbon element A is selected from porous graphite, expanded graphite, pore-creating graphite, native graphite, Delanium, mesocarbon
One or more in microsphere, soft carbon and hard carbon, the specific surface area of described carbonaceous mesophase spherules, soft carbon and hard carbon is 2-
200m2/g；Described material with carbon element B is organic cracking carbon, and described nano oxidized sub-silicon is the surface nano oxygen through modification
Changing sub-silicon grain, described nano oxidized sub-silicon is combined with described first material with carbon element by Electrostatic Absorption mode.
2. lithium ion battery negative material as claimed in claim 1, it is characterised in that described shell also includes material with carbon element C, described
Material with carbon element C is coated on the outer surface of described second material with carbon element.
3. lithium ion battery negative material as claimed in claim 2, it is characterised in that described material with carbon element C is that gas cracks carbon.
4. lithium ion battery negative material as claimed in claim 1, it is characterised in that described porous graphite, expanded graphite, make
The specific surface area of hole graphite, native graphite and Delanium is 2-200m2/g。
5. lithium ion battery negative material as claimed in claim 1 or 2, it is characterised in that described material with carbon element A accounts for described caryoplasm
The 10%-100% of amount, and/or described material with carbon element B accounts for the 3%-97% of described chitin amount.
6. lithium ion battery negative material as claimed in claim 1, it is characterised in that after described nano-silicon is modified process,
Be combined with described material with carbon element A by Electrostatic Absorption mode.
7. the preparation method of a lithium ion battery negative material, it is characterised in that comprise the following steps:
Prepare the first material with carbon element described in claim 1, as core described in claim 1；
By the modifying surface of nano oxidized sub-silicon grain is processed, by nano oxidized sub-silicon by Electrostatic Absorption mode with
Described first material with carbon element combines, it is thus achieved that the first material；
Described first material is combined with the presoma of material with carbon element B described in claim 1, it is thus achieved that the second material；
Described second material is carried out high-temperature process in an inert atmosphere, obtains described negative material.
The preparation method of a kind of lithium ion battery negative material the most as claimed in claim 7, it is characterised in that described preparing
After negative material, by chemical vapour deposition technique by material with carbon element C which deposit described in claim 2 on described negative material surface.
The preparation method of a kind of lithium ion battery negative material the most as claimed in claim 7, it is characterised in that claim 1
Described surface is embedded with the material with carbon element A of nano-silicon and is prepared by liquid phase adsorption method or chemical vapour deposition technique.
The preparation method of a kind of lithium ion battery negative material the most as claimed in claim 7, it is characterised in that described first
Material is spray drying with the presoma complex method of material with carbon element B described in claim 1.
The preparation method of 11. a kind of lithium ion battery negative materials as claimed in claim 7, it is characterised in that to nano oxygen
The method of the modifying surface changing sub-silicon grain is liquid phase grafting, is realized by grafted amino group.
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| CN112366294B (en) * | 2020-07-31 | 2022-02-15 | 万向一二三股份公司 | Graphite/silicon/carbon composite negative electrode material and preparation method thereof |
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