CN109585802A - A kind of high compacted density lithium ion battery silicon-carbon cathode material and preparation method thereof - Google Patents
A kind of high compacted density lithium ion battery silicon-carbon cathode material and preparation method thereof Download PDFInfo
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- CN109585802A CN109585802A CN201811203394.5A CN201811203394A CN109585802A CN 109585802 A CN109585802 A CN 109585802A CN 201811203394 A CN201811203394 A CN 201811203394A CN 109585802 A CN109585802 A CN 109585802A
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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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- 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
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- 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
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- Y02E60/10—Energy storage using batteries
Abstract
A kind of high compacted density lithium ion battery silicon-carbon cathode material and preparation method thereof, the negative electrode material includes carbon base body, silicon particle, the silicon particle is after ball milling activates, it is uniformly mixed with carbon matrix material, it is uniformly embedded in carbon base body after compaction moulding, then, the oxide on pickling removal silicon particle surface, forms gap between silicon particle and carbon base body.Preparation method includes being uniformly mixed after silicon particle ball milling activates with carbon matrix material, compaction moulding, broken, classification, the charing process under protective atmosphere, is washed in hydrofluoric acid solution.Silicon-carbon composite cathode material prepared by the present invention has high compacted density, and specific surface area is small, and initial coulomb efficiency is high；Through silicon-carbon cathode material prepared by the present invention, powder body compacted density is not less than 1.6g/cm3, D50=10~30 μm, specific surface area is not higher than 10m2/ g, initial coulomb efficiency are higher than 85%.Preparation process flow is simple, at low cost, is suitble to large-scale production.
Description
Technical field
The present invention relates to a kind of silicon-carbon composite anode material for lithium ion batteries and preparation method thereof, more particularly to one kind
High compacted density lithium ion battery silicon-carbon cathode material and preparation method thereof.Belong to composite material and electrochemical technology field.
Background technique
Currently, with the raising to high quality of life level requirement of development and people of society, it is environmentally protective it is novel can
Rechargeable battery attracts attention.Especially lithium ion battery, from its nineteen ninety for the first time realize commercialization since, application field from
Mobile electronic device has all obtained unprecedented development to power vehicle.But graphite cathode is limited because of its limited specific capacity
The exploitation and application of high performance lithium ion battery.
In terms of alternative negative electrode of lithium ion battery research, silica-base material is due to the lithium storage content of its superelevation by favor.
But silica-base material is during embedding de- lithium, along with and big volume expansion, blockage effect, and the electronic conductivity of its own
It is extremely low, exactly significantly limit its commercialized application.At present in terms of the study on the modification of silica-base material, main thought is pair
Silicon materials nanosizing, porous, composited processing.Nano-silicon has preferable structural stability, and porous silicon can accommodate it certainly
The volume expansion of body, but use pure silicon material still facing to capacity fade problem and poorly conductive the problem of.Thus, by silicon
With other high conductive materials carry out it is compound and carry out the design of reasonable structure be promoted its cyclical stability effective way it
One.Carbon material is widely used for the study on the modification of silicon because of its higher electron conduction, especially with the silicon of core-shell structure
Carbon is widely had an optimistic view of, and in order to avoid the volume expansion of silicon shell stress rupture problem caused by carbon shell, researcher is also logical
It crosses and silicon dioxide layer is generated by liquid phase method in silicon face, to devise the silicon-carbon core-shell structure with reserved space.At this
In structure, because there is reserved space between silicon and carbon, stress rupture of the volume expansion to carbon shell of silicon can be alleviated, but this material
Compacted density is lower, specific surface area is higher, be on the one hand unfavorable for obtaining the battery pole piece of high face carrying capacity, after being in addition also unfavorable for
The pole piece coating procedure of phase.Even if carrying out roller process in terms of later period pole piece optimization, core-shell structure stress is also easily caused to send out
Raw structural damage problem.In addition, used carbon is mostly amorphous carbon, the electric conductivity of gained Si-C composite material is unsatisfactory.
Think after present patent application person's research, the Si-C composite material with reserved space structure is solved present in silicon
One of Rational structure of critical issue, but in order to obtain high compacted density, low specific surface area, Gao Jiagong intensity, high face carrying capacity
Silicon-carbon composite cathode, need to study and develop a kind of new structure and preparation method to push the business of silicon-carbon composite cathode
Change process.
Summary of the invention
First technical problem to be solved by this invention is to provide a kind of high compacted density lithium ion battery silicon-carbon cathode
Material uses the negative electrode material system so that prepared Si-C composite material has high compacted density, low specific surface area
The capacity of standby lithium ion battery, cycle performance, high rate performance, service life are higher than common silicon-carbon cathode material.
To be solved by this invention second the technical issues of, a kind of process was simple, preparation cost is cheap, can advise greatly to provide
Mould production, high compacted density lithium ion battery silicon-carbon composite cathode with good commercial applications prospect preparation method.
In order to solve above-mentioned first technical problem, a kind of high compacted density lithium ion battery silicon-carbon cathode material of the present invention
Material, the negative electrode material includes carbon base body, silicon particle, and the silicon particle is uniformly mixed after ball milling activates with carbon matrix material,
It is uniformly embedded in carbon base body after compaction moulding, then, pickling removes the oxide on silicon particle surface, in silicon particle and carbon base body
Between form gap.
A kind of high compacted density lithium ion battery silicon-carbon cathode material of the present invention, each component mass percentage are as follows:
Silicon 5~60%；
Carbon base body 40~95%, each component quality percent and be 100%.
A kind of high compacted density lithium ion battery silicon-carbon cathode material of the present invention, the granularity of silicon particle are 30-500nm.
A kind of high compacted density lithium ion battery silicon-carbon cathode material of the present invention, the carbon base body is by carbon material and bonding agent
Composition；The mass ratio of carbon material and bonding agent is 1:0.5-3；
The carbon material is selected from least one of graphite, active carbon, carbonaceous mesophase spherules；The granularity of carbon material is 0.5-
15μm；
The bonding agent is selected from the pitch for having cohesive force to carbon and/or silicon materials, polyacrylic acid, sodium alginate, poly- inclined
At least one of vinyl fluoride；The granularity of bonding agent is 0.5-15 μm.
The silicon particle is dispersed in High-conductivity carbon substrate, and has reserved space around silicon particle, each
An at least silicon particle is dispersed in carbon base body.
The oxide layer that silicon face is washed off by the way of pickling is formed by reserved space between carbon base body and silicon particle
The volume expansion of silicon particle can be accommodated, highly conductive carbon substrate can provide three-dimensional high-speed transmission path for electronics, and facilitate shape
At stable solid electrolyte membrane.
In order to solve above-mentioned second technical problem, a kind of high compacted density lithium ion battery silicon-carbon composite cathode of the present invention
Preparation method, comprising the following steps:
Step 1: silicon particle ball milling activates
By silicon particle ball-milling treatment in air atmosphere, the activation silicon particle of surface oxidation is obtained；
Step 2: silicon, carbon are compound
Activation silicon particle that the first step obtains, carbon matrix material are uniformly mixed, is crushed, is classified after compaction moulding, classification
Afterwards, D is taken50=12~34 μm of powder carries out the charing process under protective atmosphere, obtains silicon-carbon composite powder；The carbon base body material
Material is made of carbon material and bonding agent；
Step 3: preparing silicon-carbon composite cathode
It disperses the silicon-carbon composite powder that second step obtains in hydrofluoric acid solution and washs, removal activation silicon particle surface
After oxide, clear water rinsed clean, drying obtain having the lithium ion battery silicon-carbon in gap compound between silicon particle and carbon base body
Cathode.
A kind of preparation method of high compacted density lithium ion battery silicon-carbon composite cathode of the present invention, in the first step, at ball milling
When reason, 50~500r/min of drum's speed of rotation, Ball-milling Time is 5~12h.
A kind of preparation method of high compacted density lithium ion battery silicon-carbon composite cathode of the present invention in second step, activates silicon
When particle, carbon base body mixing, each component mass percent are as follows:
Activate silicon particle 5~60%；
Carbon base body 40~95%.
A kind of preparation method of high compacted density lithium ion battery silicon-carbon composite cathode of the present invention, the carbon base body is by carbon materials
Material is formed with powder bonding agent；The mass ratio of carbon material and powder bonding agent is 1:0.5-3；
The carbon material is selected from least one of graphite, active carbon, carbonaceous mesophase spherules；The granularity of carbon material is 0.5-
15μm；
The bonding agent is selected from the pitch for having cohesive force to carbon and/or silicon materials, polyacrylic acid, sodium alginate, poly- inclined
At least one of vinyl fluoride；The granularity of bonding agent is 0.5-15 μm；
A kind of preparation method of high compacted density lithium ion battery silicon-carbon composite cathode of the present invention in second step, activates silicon
Particle, carbon base body are mixed using batch mixer；After mixing, it is sent into double screw extruder extrusion sheet or is placed in mixing
It is kneaded out bulk in machine, then is compacted by roll squeezer.
A kind of preparation method of high compacted density lithium ion battery silicon-carbon composite cathode of the present invention, be crushed in second step, point
Grade be the material base of compaction moulding is placed in crusher be crushed, classification processing；D is taken after classification50=12~34 μm of powders.
A kind of preparation method of high compacted density lithium ion battery silicon-carbon composite cathode of the present invention, in second step, at charing
Reason is that the powder after classification is heated to 500~1200 DEG C, 0.5~4h is kept the temperature, realizes powder adhesive under protective atmosphere
Charing；During protective atmosphere is hydrogen, is a kind of or several in argon gas, nitrogen.
A kind of preparation method of high compacted density lithium ion battery silicon-carbon composite cathode of the present invention, in third step, by second
It walks obtained silicon-carbon composite powder to be scattered in the hydrofluoric acid solution that mass concentration is 2~40%, agitator treating 0.5~4h is molten
Solve the silicon oxide layer of activated silica particle surface, silicon-carbon composite powder after pickling water floats after washes clean in 80~120 DEG C
Drying process 10~for 24 hours, obtain carbon base body lithium ion battery silicon-carbon composite negative pole.
In described high compacted density lithium ion battery silicon-carbon cathode material and preparation method thereof, silicon particle is carried out first
Ball-milling treatment under air atmosphere, in mechanical milling process, silicon particle surface-active is high, it can be achieved that surface oxidation, the oxide layer
Pickling removal is carried out in the later period, reserved space can be provided for the volume change of silicon；By pretreated silicon particle, graphite, bonding
Agent carries out mixing, extrusion molding, compacting, and the graphite of use has the electric conductivity and electrochemical stability of superelevation, can be promoted multiple
The electron transport ability and electrochemical stability of condensation material, used binder are carbon containing inorganic matter or organic matter, bonding
Agent not only can firmly be wrapped up silicon particle, graphite, but also be pyrolyzed in later period carbonisation, can be converted into
Carbon becomes active component.
High compacted density lithium ion battery silicon-carbon cathode material by adopting the above technical scheme and preparation method thereof, it is carbon-based
Bottom is formed by binder pyrolytic carbon package graphite, has highly conductive, high stability, one or more silicon particles are wrapped up it
In, and the silicon particle wrapped up is dispersed in highly conductive carbon substrate, thus it is possible, on the one hand, the volume expansion of silicon particle is
It is limited in the carbon substrate being compacted, and there is reserved expansion space around it, still further aspect, High-conductivity carbon substrate can
The volume expansion bring stress due to silicon is preferably absorbed, further prevents the volume expansion of silicon broken to the stress of carbon substrate
It is bad, thus, it ensure that the structural intergrity and stability of carbon substrate.The present invention has the advantage that compared with present technology
1. being reserved with expansion space around silicon particle and silicon materials being scattered in the carbon substrate of compacting, carbon substrate not only may be used
To receive the volume expansion of silicon particle to guarantee structural stability, and be conducive to electron-transport；
2. selected carbon substrate is made of graphite and binder pyrolytic carbon, embedding de- lithium characteristic is all had, is helped to improve
The capacity of composite material；
3. carbon substrate can prevent electrolyte to its internal infiltration, the internal carbon substrate through being compacted can be prevented by silicon
Volume expansion and destruction of the bring stress to carbon substrate, therefore, stable carbon substrate will be helpful to its external solid electrolyte
The formation of film improves the coulombic efficiency and cycle life of composite material；
4. composite material preparation flow is simple, is easy to large-scale production.
In conclusion silicon-carbon composite cathode material prepared by the present invention has high compacted density, specific surface area is small, for the first time
Coulombic efficiency is high；Through silicon-carbon cathode material prepared by the present invention, powder body compacted density is not less than 1.6g/cm3, D50=10~
30 μm, specific surface area is not higher than 10m2/ g, initial coulomb efficiency are higher than 85%.Preparation process flow is simple, at low cost, is suitble to big
Large-scale production.
Detailed description of the invention
Attached drawing 1 is the scanning electron microscope (SEM) photograph of composite negative pole material prepared by the embodiment of the present invention 1.
Attached drawing 2 is the scanning electron microscope (SEM) photograph of composite negative pole material prepared by the embodiment of the present invention 2.
Attached drawing 3 is the scanning electron microscope (SEM) photograph of composite negative pole material prepared by the embodiment of the present invention 3.
Attached drawing 4 is the transmission electron microscope picture of composite negative pole material prepared by the embodiment of the present invention 3.
Attached drawing 5 is composite negative pole material model structure schematic diagram of the present invention.
Respectively it can be seen that the size of resulting materials is 10~30 μm from attached drawing 1,2,3, the carbon material of addition influences multiple
Close the pattern of cathode.
Such as attached drawing 1, carbon material used by embodiment 1 is carbonaceous mesophase spherules, its own is spherical shape, is formed by compound
Negative electrode material is spherical shape；
Attached drawing 2, carbon material used by embodiment 2 are artificial graphite, its own is irregular shape, is formed by compound
Negative electrode material is irregular shape；
Attached drawing 3, carbon material used by embodiment 3 are natural flake graphite, its own is flake shape, are formed by multiple
Closing negative electrode material is bulk.
From attached drawing 4 it can be seen that significantly reserving pore structure around silicon particle.
Specific embodiment
Invention is further described in detail combined with specific embodiments below, but the invention is not limited to following implementations
Example.
Compacted density is measured using tap density meter in the embodiment of the present invention, comparative example, and specific surface area uses specific surface area
Tester test, resulting materials initial coulomb efficiency are by being coated resulting materials, after button cell assembly, in button
It is measured on battery electrochemical tester.
Embodiment 1:
(1) taking 1g average grain diameter is the silicon particle of 50nm, and it is 200r/ that 20g agate, which is added, and carries out revolving speed in agate mortar
The ball-milling treatment 8h of min.
(2) silicon particle, carbonaceous mesophase spherules (1g), the Kynoar (0.2g) after ball milling are placed in batch mixer and are carried out
It is uniformly mixed, and mixed material is sent into double screw extruder extrusion sheet, then be compacted by roll squeezer.
(3) upper step resulting compacting material is placed in crusher be crushed, classification is handled, control product D50=20~30
μm, fine powder is placed in double screw extruder extrusion sheet, then roll-in compacting again；Coarse powder is crushed again, is classified.
(4) material after the classification of upper step is heat-treated under nitrogen atmosphere, heat treatment temperature is 800 DEG C, soaking time
For 2h.
(5) it disperses the obtained sample of upper step in the hydrofluoric acid solution that concentration is 10%, stirs 1h, then carried out sufficiently with water
It washs and drying and processing for 24 hours, obtains high compacted density lithium ion battery silicon-carbon cathode material in 120 DEG C of drying box.Gained
The compacted density of composite material is 1.8g/cm3, specific surface area 4.1m2/ g, initial coulomb efficiency are higher than 92% (0.2C).
Embodiment 2:
(1) taking 1g average grain diameter is the silicon particle of 100nm, and it is 400r/ that 20g agate, which is added, and carries out revolving speed in agate mortar
The ball-milling treatment 5h of min.
(2) silicon particle, artificial graphite (1g), the pitch (0.5g) after ball milling are placed in batch mixer carry out it is uniformly mixed,
And mixed material is sent into double screw extruder extrusion sheet, then be compacted by roll squeezer.
(3) upper step resulting compacting material is placed in crusher be crushed, classification is handled, control product D50=20~30
μm, fine powder is placed in double screw extruder extrusion sheet, then roll-in compacting again；Coarse powder is crushed again, is classified.
(4) by upper step classification after material be placed in tube furnace, be heat-treated under argon atmosphere, heating rate be 5 DEG C/
Min, heat treatment temperature are 900 DEG C, soaking time 2h.
(5) it disperses the obtained sample of upper step in the hydrofluoric acid solution that concentration is 20%, stirs 0.5h, then filled with water
Divide washing and drying and processing for 24 hours, obtains high compacted density lithium ion battery silicon-carbon cathode material in 120 DEG C of drying box.Institute
The compacted density for obtaining composite material is 1.7g/cm3, specific surface area 3.6m2/ g, initial coulomb efficiency 89% (0.2C).
Embodiment 3:
(1) taking 1g average grain diameter is the silicon particle of 500nm, and it is 500r/ that 20g agate, which is added, and carries out revolving speed in agate mortar
The ball-milling treatment 10h of min.
(2) silicon particle, natural flake graphite (1.2g), the polyacrylic acid (0.5g) after ball milling are placed in batch mixer and are carried out
It is uniformly mixed, and mixed material is sent into mixer and is kneaded out bulk, then is compacted by roll squeezer.
(3) upper step resulting compacting material is placed in crusher be crushed, classification is handled, control product D50=15~30
μm, fine powder is placed in double screw extruder extrusion sheet, then roll-in compacting again；Coarse powder is crushed again, is classified.
(4) material after the resulting classification of upper step is placed in tube furnace, is heat-treated under argon atmosphere, heating speed
Rate is 5 DEG C/min, and holding temperature is 900 DEG C, soaking time 4h.
(5) it disperses the obtained sample of upper step in the hydrofluoric acid solution that concentration is 20%, stirs 0.5h, then filled with water
Divide washing and drying and processing for 24 hours, obtains high compacted density lithium ion battery silicon-carbon cathode material in 120 DEG C of drying box.Institute
The compacted density for obtaining composite material is 1.9g/cm3, specific surface area 2.6m2/ g, initial coulomb efficiency 91% (0.2C).
Embodiment 4:
(1) taking 1g average grain diameter is the silicon particle of 100nm, and it is 500r/ that 20g agate, which is added, and carries out revolving speed in agate mortar
The ball-milling treatment 10h of min.
(2) silicon particle, graphite (0.8g), the sodium alginate (0.5g) after ball milling are placed in batch mixer and mix
It is even, and mixed material is sent into mixer and is kneaded out bulk, then is compacted by roll squeezer.
(3) upper step resulting compacting material is placed in crusher be crushed, classification is handled, control product D50=15~30
μm, fine powder is placed in double screw extruder extrusion sheet, then roll-in compacting again；Coarse powder is crushed again, is classified.
(4) material after the resulting classification of upper step is placed in tube furnace, is heat-treated under nitrogen atmosphere, heating speed
Rate is 10 DEG C/min, and holding temperature is 800 DEG C, soaking time 5h.
(5) it disperses the obtained sample of upper step in the hydrofluoric acid solution that concentration is 20%, stirs 0.5h, then filled with water
Divide washing and drying and processing for 24 hours, obtains high compacted density lithium ion battery silicon-carbon cathode material in 120 DEG C of drying box.Institute
The compacted density for obtaining composite material is 1.7g/cm3, specific surface area 3.2m2/ g, initial coulomb efficiency 90% (0.2C).
Embodiment 5:
(1) taking 1g average grain diameter is the silicon particle of 200nm, and it is 500r/ that 20g agate, which is added, and carries out revolving speed in agate mortar
The ball-milling treatment 10h of min.
(2) silicon particle, graphite (0.5g), the sodium alginate (0.5g) after ball milling are placed in batch mixer and mix
It is even, and mixed material is sent into mixer and is kneaded out bulk, then is compacted by roll squeezer.
(3) upper step resulting compacting material is placed in crusher be crushed, classification is handled, control product D50=20~30
μm, fine powder is placed in double screw extruder extrusion sheet, then roll-in compacting again；Coarse powder is crushed again, is classified.
(4) material after the resulting classification of upper step is placed in tube furnace, is placed in mixture after stirring 4h at room temperature
It in tube furnace, is heat-treated under argon atmosphere, heating rate is 5 DEG C/min, and holding temperature is 900 DEG C, and soaking time is
4h。
(5) it disperses the obtained sample of upper step in the hydrofluoric acid solution that concentration is 20%, stirs 0.5h, then filled with water
Divide washing and drying and processing for 24 hours, obtains high compacted density lithium ion battery silicon-carbon cathode material in 120 DEG C of drying box.Institute
The compacted density for obtaining composite material is 1.7g/cm3, specific surface area 3.2m2/ g, initial coulomb efficiency 90% (0.2C).
Comparative example 1: without compaction treatment
(1) taking 1g average grain diameter is the silicon particle of 100nm, and it is 500r/ that 20g agate, which is added, and carries out revolving speed in agate mortar
The ball-milling treatment 10h of min.
(2) silicon particle, graphite (0.8g), the sodium alginate (0.5g) after ball milling are placed in batch mixer carry out it is uniformly mixed
Afterwards, it is placed in tube furnace, is heat-treated under nitrogen atmosphere, heating rate is 10 DEG C/min, and holding temperature is 800 DEG C, is protected
The warm time is 5h.
(3) it disperses the obtained sample of upper step in the hydrofluoric acid solution that concentration is 20%, stirs 0.5h, then filled with water
Divide washing and drying and processing for 24 hours, obtains silicon-carbon composite cathode material in 120 DEG C of drying box.The compacting of gained composite material
Density is 0.7g/cm3, specific surface area 105m2/ g, initial coulomb efficiency 76% (0.2C).
Comparative example 2: binder is not added
(1) taking 1g average grain diameter is the silicon particle of 200nm, and it is 500r/ that 20g agate, which is added, and carries out revolving speed in agate mortar
The ball-milling treatment 10h of min.
(2) silicon particle, the graphite (0.5g) after ball milling are placed in batch mixer and carry out uniformly mixed, and mixed material sent
Enter and be kneaded out bulk in mixer, then is compacted by roll squeezer.
(3) upper step resulting compacting material is placed in crusher be crushed, classification is handled, control product D50=20~30
μm, fine powder is placed in double screw extruder extrusion sheet, then roll-in compacting again；Coarse powder is crushed again, is classified.
(4) material after the resulting classification of upper step is placed in tube furnace, is placed in mixture after stirring 4h at room temperature
It in tube furnace, is heat-treated under argon atmosphere, heating rate is 5 DEG C/min, and holding temperature is 900 DEG C, and soaking time is
4h。
(5) it disperses the obtained sample of upper step in the hydrofluoric acid solution that concentration is 20%, stirs 0.5h, then filled with water
Divide washing and drying and processing for 24 hours, obtains lithium ion battery silicon-carbon cathode material in 120 DEG C of drying box.Gained composite material
Compacted density be 1.3g/cm3, specific surface area 55m2/ g, initial coulomb efficiency 78% (0.2C).
Comparative example 3: carbon material is not added
(1) taking 1g average grain diameter is the silicon particle of 500nm, and it is 500r/ that 20g agate, which is added, and carries out revolving speed in agate mortar
The ball-milling treatment 10h of min.
(2) silicon particle, the polyacrylic acid (0.5g) after ball milling are placed in batch mixer carry out it is uniformly mixed, and by mixing
Material is sent into mixer and is kneaded out bulk, then is compacted by roll squeezer.
(3) upper step resulting compacting material is placed in crusher be crushed, classification is handled, control product D50=15~30
μm, fine powder is placed in double screw extruder extrusion sheet, then roll-in compacting again；Coarse powder is crushed again, is classified.
(4) material after the resulting classification of upper step is placed in tube furnace, is heat-treated under argon atmosphere, heating speed
Rate is 5 DEG C/min, and holding temperature is 900 DEG C, soaking time 4h.
(5) it disperses the obtained sample of upper step in the hydrofluoric acid solution that concentration is 20%, stirs 0.5h, then filled with water
Divide washing and drying and processing for 24 hours, obtains lithium ion battery silicon-carbon cathode material in 120 DEG C of drying box.Gained composite material
Compacted density be 0.9g/cm3, specific surface area 102.4m2/ g, initial coulomb efficiency 75% (0.2C).
By comparing the measured data of embodiment 1-5 and comparative example 1,2, it can be deduced that, by adding carbon in carbon substrate
Material, addition binder carry out compacting pretreatment process, can effectively optimize the physics and chemical property of material, especially material
The compacted density and initial coulomb efficiency of material, silicon-carbon cathode material prepared by the present invention, powder body compacted density is not less than
1.6g/cm3, D50=10~30 μm, specific surface area is not higher than 10m2/ g, initial coulomb efficiency are higher than 85%.
Claims (10)
1. a kind of high compacted density lithium ion battery silicon-carbon cathode material, the negative electrode material includes carbon base body, silicon particle, described
Silicon particle is uniformly mixed after ball milling activates with carbon matrix material, is uniformly embedded in carbon base body after compaction moulding, then, acid
The oxide except silicon particle surface is washed away, forms gap between silicon particle and carbon base body.
2. a kind of high compacted density lithium ion battery silicon-carbon cathode material according to claim 1, each component quality percentage
Content are as follows:
Silicon 5~60%；
Carbon base body 40~95%, each component quality percent and be 100%.
3. a kind of high compacted density lithium ion battery silicon-carbon cathode material according to claim 2, it is characterised in that: silicon
The granularity of grain is 30-500nm；
The carbon base body is made of carbon material and bonding agent；The mass ratio of carbon material and bonding agent is 1:0.5-3；
The carbon material is selected from least one of graphite, active carbon, carbonaceous mesophase spherules；The granularity of carbon material is 0.5-15 μ
m；
The bonding agent is selected from pitch, polyacrylic acid, sodium alginate, the polyvinylidene fluoride for having cohesive force to carbon and/or silicon materials
At least one of alkene；The granularity of bonding agent is 0.5-15 μm.
4. a kind of preparation method of high compacted density lithium ion battery silicon-carbon composite cathode, comprising the following steps:
Step 1: silicon particle ball milling activates
By silicon particle ball-milling treatment in air atmosphere, the activation silicon particle of surface oxidation is obtained；
Step 2: silicon, carbon are compound
Activation silicon particle that the first step obtains, carbon matrix material are uniformly mixed, is crushed, is classified after compaction moulding, after classification, take
D50=12~34 μm of powder carries out the charing process under protective atmosphere, obtains silicon-carbon composite powder；The carbon matrix material by
Carbon material and bonding agent form；
Step 3: preparing silicon-carbon composite cathode
It disperses the silicon-carbon composite powder that second step obtains in hydrofluoric acid solution and washs, the oxidation on removal activation silicon particle surface
After object, clear water rinsed clean, drying obtain the lithium ion battery silicon-carbon Compound Negative between silicon particle and carbon base body with gap
Pole.
5. a kind of preparation method of high compacted density lithium ion battery silicon-carbon composite cathode according to claim 4, special
Sign is: in the first step, when ball-milling treatment, drum's speed of rotation is 50~500r/min, and Ball-milling Time is 5~12h.
6. a kind of preparation method of high compacted density lithium ion battery silicon-carbon composite cathode according to claim 4, special
Sign is: in second step, when activation silicon particle, carbon base body mix, and each component mass percent are as follows:
Activate silicon particle 5~60%；
Carbon base body 40~95%.
7. a kind of preparation method of high compacted density lithium ion battery silicon-carbon composite cathode according to claim 6, special
Sign is: in second step, the carbon base body is made of carbon material and powder bonding agent；The mass ratio of carbon material and bonding agent is 1:
0.5-3；
The carbon material is selected from least one of graphite, active carbon, carbonaceous mesophase spherules；The granularity of carbon material is 0.5-15 μ
m；
The bonding agent is selected from pitch, polyacrylic acid, sodium alginate, the polyvinylidene fluoride for having cohesive force to carbon and/or silicon materials
At least one of alkene；The granularity of powder bonding agent is 0.5-15 μm.
8. a kind of preparation method of high compacted density lithium ion battery silicon-carbon composite cathode according to claim 7, special
Sign is: in second step, activation silicon particle, carbon base body are mixed using batch mixer；After mixing, it is sent into twin-screw extrusion
Machine extrusion sheet is placed in mixer and is kneaded out bulk, then is compacted by roll squeezer；The material base of compaction moulding is set
It is crushed in crusher, classification processing；D is taken after classification50=12~34 μm of powders.
9. a kind of preparation method of high compacted density lithium ion battery silicon-carbon composite cathode according to claim 8, special
Sign is: in second step, charing process is the powder after classification to be heated to 500~1200 DEG C, heat preservation under protective atmosphere
0.5~4h realizes the charing of powder adhesive；During protective atmosphere is hydrogen, is a kind of or several in argon gas, nitrogen.
10. a kind of system of high compacted density lithium ion battery silicon-carbon composite cathode according to claim 4-8 any one
Preparation Method, it is characterised in that: in third step, dispersing mass concentration for the silicon-carbon composite powder that second step obtains is 2~40%
Hydrofluoric acid solution in, 0.5~4h of agitator treating dissolves the silicon oxide layer of activated silica particle surface, and the silicon-carbon after pickling is compound
Powder with water float washes clean after in 80~120 DEG C drying process 10~for 24 hours, it is compound to obtain carbon base body lithium ion battery silicon-carbon
Cathode.
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