CN107204431A - A kind of lithium ion battery anode active material and preparation method thereof, negative pole and battery comprising the negative active core-shell material - Google Patents
A kind of lithium ion battery anode active material and preparation method thereof, negative pole and battery comprising the negative active core-shell material Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- 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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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
Negative pole and battery the invention provides a kind of lithium ion battery anode active material and preparation method thereof, comprising the negative active core-shell material, the negative active core-shell material includes graphite particle, and the silicon carbide composite particles on graphite particle surface are dispersed in, the exposed surface area of the graphite particle is the 80% ~ 98% of graphite particle total surface area.The lithium ion battery anode active material that the present invention is provided solve in the prior art lithium ion battery in charge and discharge process, internal layer graphite particle is with outer layer silicon carbide composite particles composite due to expanding the problems such as uneven caused outer layer silicon carbon material ftractures and come off, good electrical contact is maintained, improves cycle performance of battery.
Description
Technical field
The present invention relates to field of lithium ion battery, and in particular to a kind of lithium ion battery anode active material and its preparation side
Method, negative pole and battery comprising the negative active core-shell material.
Background technology
Now widely used negative electrode of lithium ion battery is based on graphite, and the theoretical capacity of graphite is 372mAh/g, charge and discharge
Platform is good in electric process, and current potential is low, is ideal negative material.Extraordinary effect is achieved in past application
Really.However, as many new opplications of lithium battery, the charcoal class material such as graphite progressively exposes some shortcomings：Finite capacity, big times
Rate charging and discharging capabilities are relatively low, poor performance at low temperatures etc..Especially large current charge performance is not good, because the voltage platform of graphite is low,
80mV is differed only by with the current potential of lithium metal, the current potential of lithium is easily reached in large current charge and occurs the analysis of lithium metal
Go out, cause potential safety hazard.
Theoretical specific capacity highest of the Si sills in the material that people up to now are studied, its formed alloy be
LixSi, x scope are 0-4.4, and the theoretical specific capacity of pure silicon is 4200mAh/g, much larger than the theoretical capacity of graphite, and silicon
Alloy has a solvation unlike graphite, low intercalation potential, low atomic wts, high-energy-density and in Li-Si alloys
High Li molar fractions, more other metals and material have higher stability and got most of the attention, it is considered to be most promising Gao Rong
The lithium ion battery negative material of amount.However, silicium cathode will undergo serious volume due to it in embedding, the de- cyclic process of lithium
Expansion and contraction, cause destruction and the pulverization of material structure, so as to cause the decline of electrode cycle performance, limit its business
Change application.
In order to solve silicium cathode material, easily generation stress cracking causes volumetric expansion to cause circulation in charge and discharge process
The problem of performance degradation, mainly there are three kinds of ameliorative ways at present：Reduce the particle diameter of active nano silicon grain, prepare nanometer materials
To reduce the internal stress of Volume Changes；Mesophase material substitution simple metal is prepared with active metal or inactive metal；Using
Carbon coating prepares the methods such as Core-shell structure material.
Patent CN201310566652.7 mentions a kind of graphite silicon composite lithium ion battery cathode material and preparation method thereof,
Propose to bond graphite and silicon by the use of high acrylonitrile content polymerizing microballoons as pyrolysis carbon matrix precursor, be self-assembled into larger spheric granules
Si-C composite material.Although the product prepared has carbon left high, mix homogeneous, silicon is firmly bonded with graphite, long-term storage with
Discharge and recharge advantage difficult for drop-off.But the following shortcoming that such scheme is still suffered from：1st, granulated using the mode of spray drying,
The carbon ball internal voids of preparation are more, and tap density and compacted density are low, cause volume and capacity ratio relatively low, and practical application is poor.
2nd, in spherical silicon carbon material, silicon is filled primarily with the spherical structure of graphite particle formation, largely sticks to graphite surface, is influenceed
Bond effect between graphite particle.3rd, material is in charge and discharge process, and structural stability is difficult to ensure, easily occurs rupture, powder
Change, the problems such as cycle performance declines.
Patent CN201210169022 discloses a kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof, knot
Structure is using graphite kernel as carrier, and silicon nanoparticle is coated on graphite kernel carrier surface, and the program is improved to a certain extent
The cycle performance of Si-C composite material.But scheme has the following disadvantages：In charge and discharge process, the volume deformation of silicon 300% causes
Outer layer silicon-carbon composite shell has a larger volume deformation, the Volume Changes of internal layer graphite 6%, the volume deformation that both differ greatly,
Cause to produce huge stress between internal layer and outer shell, the problems such as being easily caused outer layer silicon-carbon composite shell cracking and come off,
In the process, the intrusion of electrolyte, the generation of SEI films is further exacerbated by this process, cause collector make electrical contact with forfeiture and
The decline of cycle performance.
The content of the invention
Lithium ion battery is in charge and discharge process in order to solve in the prior art by the present invention, internal layer graphite particle and outer layer silicon
Carbon composite particles composite is due to the problems such as the uneven caused outer layer silicon carbon material of expansion ftractures and come off, maintaining good electricity
Contact, improves cycle performance of battery；There is provided a kind of lithium ion battery anode active material, including graphite particle, and it is scattered
Silicon carbide composite particles on graphite particle surface, the exposed surface area of the graphite particle for graphite particle total surface area 80% ~
98%。
Present invention also offers a kind of preparation method of lithium ion battery anode active material, the preparation method includes：
（1）Silicon nanoparticle is mixed with the first organic carbon source, it is scattered after be carbonized obtaining silicon carbide composite particles；
（2）By step（1）In silicon carbide composite particles and the second organic carbon source it is heated mediate, obtain Surface coating second organic
The silicon carbide composite particles of carbon source；
（3）By step（2）The silicon carbide composite particles of the middle organic carbon source of Surface coating second are carbonized after being mixed with graphite particle,
Obtain negative active core-shell material.
The present invention also provides a kind of negative electrode of lithium ion battery, and the negative pole includes negative active core-shell material described herein.
Finally, the invention provides a kind of lithium ion battery, the negative active core-shell material used in the negative pole is the present invention
The negative electrode active material.
In the lithium ion battery anode active material that the present invention is provided, silicon carbide composite particles are dispersed in graphite particle surface,
Simultaneously in silicon carbide composite particles, silicon nanoparticle is dispersed in carbon ball；Silicon carbide composite particles pass through carbon-coating with graphite particle
Combine to form stable structure, the contact surface of graphite particle and silicon carbide composite particles is smaller, it is possible to prevente effectively from due to discharge and recharge
During different occurred contact surface crackings of graphite particle and silicon carbide composite particles overall deformation and the problems such as come off, maintenance is good
Good electrical contact.Graphite particle surface major part region is exposed can to improve material electrical contact, while silicon carbide composite particles and stone
The relatively large volume difference of black particle, silicon carbide composite particles can effectively utilize the space between graphite particle, reduce to graphite
The influence of particle and collector, maintains good cycle performance.
The preparation method of lithium ion battery anode active material proposed by the present invention, by the way that silicon nanoparticle is had with first
After the mixing of machine carbon source be carbonized obtaining silicon carbide composite particles so that in silicon carbide composite particles, silicon nanoparticle can uniformly divide
It is dispersed in carbon ball；In addition, the first organic carbon source and the second organic carbon source escape shape in gaseous form in thermal decomposition process light component
Into a large amount of pore space structures can further alleviate the volumetric expansion of silicon nanoparticle；Meanwhile, the carbonization energy of the second organic carbon source
Enough so that silicon carbide composite particles stick to the surface of graphite particle by the second organic carbon source carbon-coating to be formed that is carbonized, what is obtained is negative
Pole active material can maintain stable structure, it is to avoid the problems such as rupture and efflorescence occur.
Brief description of the drawings
Fig. 1 is A1 electromicroscopic photographs in embodiment 1（X5000 multiplying powers）；
Fig. 2 is C1 electromicroscopic photographs in embodiment 1（X1000 multiplying powers）；
Fig. 3 is C1 electromicroscopic photographs in embodiment 1（X5000 multiplying powers）；
Fig. 4 is C2 electromicroscopic photographs in embodiment 2（X1000 multiplying powers）；
Fig. 5 is C2 electromicroscopic photographs in embodiment 2（X5000 multiplying powers）.
Embodiment
In order that technical problem solved by the invention, technical scheme and beneficial effect are more clearly understood, below to this
Invention is further elaborated.
The invention provides a kind of lithium ion battery anode active material, including graphite particle, and it is dispersed in graphite
The silicon carbide composite particles on grain surface, the exposed surface area of the graphite particle is the 80% ~ 98% of graphite particle total surface area.It is described
Silicon carbide composite particles are the carbon ball for being dispersed with silicon nanoparticle.
It is preferred that, the exposed surface area of graphite particle is the 80% ~ 98% of graphite particle total surface area, more preferably 85% ~
90%, no silicon carbide composite particles adhesion.Graphite particle surface major part region is exposed can to improve material electrical contact, improve afflux
The stabilization of body is so as to improve cycle performance.
It is preferred that, the average grain diameter of graphite particle is 10um ~ 25um, more preferably 15 ~ 20um.The raising of particle diameter can be with
The side reaction of graphite particle is reduced, efficiency first is improved.Gap and the particle diameter of silicon carbide composite particles between graphite particle are mutually fitted
Should.It is possible to prevente effectively to electrical contact between graphite particle and the influence of collector.The particle diameter of graphite particle is too small, graphite particle
Between gap it is too small, be not enough to accommodate the larger silicon carbide composite particles of relative grain size.The particle diameter of graphite particle is excessive, graphite particle
Unit Weight under, number of gaps is significantly reduced, and is not enough to be filled up completely with silicon carbide composite particles.Partial particulate is had to duplicate
The problems such as stacking, influence cycle performance.
It is preferred that, the average grain diameters of silicon carbide composite particles is the 1% ~ 10% of graphite particle average grain diameter, more preferably 2% ~
5%.Silicon carbide composite particles are adapted with graphite particle gap length, can be avoided to electrical contact and collector between graphite particle
Influence.Particle diameter is too small, the specific surface area meeting showed increased of silicon carbide composite particles, increase and the contact surface of electrolyte, secondary anti-
It should substantially increase, the problems such as efficiency declines first occur.Particle diameter is excessive, and silicon carbide composite particles deformation is big, easily occurs coming off, powder
The problems such as change, the influence to collector can also be significantly increased.
It is preferred that, it is that silicon carbide composite particles number ratio of the graphite particle with being dispersed in graphite particle surface is 1：1~1：
100, more preferably 1：5~1：20, now the matching of silicon carbide composite particles and graphite particle is preferable；Ratio is too low can be bright
Aobvious to reduce reversible capacity, ratio is excessive, the electrical contact between influence graphite particle, influences larger to collector, under cycle performance
Drop.
It is preferred that, the porosity of silicon carbide composite particles is 15% ~ 60%, more preferably 3% ~ 60%.Make internal porous, can
Expanded with further alleviate.
The silicon carbide composite particles include carbon ball and silicon nanoparticle, and the silicon nanoparticle is distributed in carbon ball.Silicon-carbon
Composite particles are attached to the surface of graphite particle, form overall structure.It can avoid in charge and discharge process, due to internal layer graphite
Grain and outer layer Si-C composite material due to expansion it is uneven caused by outer layer silicon carbon material cracking and the problems such as come off, remain good
Electrical contact.
Present invention also offers a kind of preparation method of lithium ion battery anode active material, its preparation technology is as follows：
（1）By silicon nanoparticle with there is the first machine carbon source to mix, it is scattered after be carbonized obtaining silicon carbide composite particles；
（2）By step（1）In silicon carbide composite particles and the second organic carbon source it is heated mediate, obtain Surface coating second organic
The silicon carbide composite particles of carbon source；
（3）By step（2）The silicon carbide composite particles of the middle organic carbon source of Surface coating second are carbonized after being mixed with graphite particle,
Obtain negative active core-shell material.
It is preferred that, the average grain diameter of silicon nanoparticle is 30nm ~ 200nm, more preferably 30 ~ 100nm.Preferred scope
Interior, the particle diameter of silicon nanoparticle is smaller, and volume deformation is small in charge and discharge process, and cycle performance can be significantly improved.
It is preferred that, the first organic carbon source and the second organic carbon source are each independently selected from asphalt, coal tar pitch, sucrose, Portugal
One or more in grape sugar, starch, phenolic resin and epoxy resin.It is preferred that, pitch.
It is preferred that, the step（1）Middle carburizing temperature is 500 DEG C ~ 1200 DEG C；The silicon nanoparticle and the first organic carbon source
Mass ratio be 1：5 ~ 2：1.Can be with fine dispersion in the carbon ball of formation of the silicon nanoparticle after final carbonization, possessing has good
Good structural strength.
It is preferred that, the step（2）Middle heating-up temperature is 100 DEG C ~ 250 DEG C；The silicon carbide composite particles and the second organic carbon
The mass ratio in source is 1：3 ~ 4：1.Second organic carbon source can provide enough adhesions, combine silicon carbide composite particles
The surface of graphite particle.
It is preferred that, the step（3）Middle carburizing temperature is 750 DEG C ~ 1200 DEG C；The silicon carbide composite particles and graphite particle
Mass ratio is 1：20 ~ 1：5.Reversible capacity and cycle performance can be taken into account, possesses higher reversible capacity and preferably circulation
Performance.
The refinement of preparation method：
The silicon nanoparticle and the first organic carbon source that step 1, selection particle diameter are 30nm ~ 200nm are through ball milling（Ball-milling technology in experiment
Carry out under an inert atmosphere, specified otherwise is not done subsequently）After scattered, the mass ratio of silicon nanoparticle and the first organic carbon source is
1：5 ~ 2：1, Ball-milling Time 2h, rotational speed of ball-mill 250r/min.Under an inert atmosphere, heated up with 5 DEG C/min, 500 DEG C ~ 1200 DEG C
Lower roasting 4h.Again through 210r/min, 1h ball mill grindings.The particle diameter for obtaining silicon carbide composite particles is 0.1 μm ~ 2.5 μm.
Step 2, the second organic carbon source is heated to 100 DEG C ~ 250 DEG C, the second organic carbon source is converted into liquid condition, plus
Enter silicon carbide composite particles, the mass ratio of silicon carbide composite particles and the second organic carbon source is 1：3 ~ 4：1, through at 100 DEG C ~ 250 DEG C
Stirring 1h is mediated, is taken out after cooling, size-reduced machine is crushed, the silicon carbide composite particles for being coated with carbon-coating are made.
Step 3, the graphite particle for being 10um ~ 25um by silicon carbide composite particles and particle diameter that carbon-coating is coated with step 2 make
High speed mixer 300r/min is used, it is 1 to be coated with the silicon carbide composite particles of carbon-coating and the ratio of graphite particle：20 ~ 1：5.It is mixed
Expect 30min, make to be uniformly distributed.It is placed in inert atmosphere stove, is heated up with 5 DEG C/min, 750 DEG C ~ 1200 DEG C roasting 1h.Ground sieve
Get final products, the exposed surface area of the graphite particle is the 98% of graphite particle total surface area, labeled as C1.
It is preferred that, one or more of the inert gas used in the inert atmosphere in nitrogen, argon gas, helium are entered
One step is preferably nitrogen.
High-temperature roasting under an inert atmosphere, the second organic carbon source is pyrolyzed the table for making silicon carbide composite particles be fixed on graphite particle
Face, forms stable structure.Under the structure, silicon carbide composite particles are dispersed in carbon ball due to silicon nanoparticle, inside it
There is pore space structure.
The present invention provides a kind of negative electrode of lithium ion battery, and the negative pole includes negative current collector and negative active core-shell material,
Negative active core-shell material includes negative active core-shell material, negative electrode binder, and including for the being also an option that property of negative active core-shell material is negative
Pole conductive agent, the cathode conductive agent is this area conventional anode conductive agent；The preparation method of the negative pole is that this area is conventional
The preparation method of negative electrode of lithium ion battery, including negative electrode active material, negative electrode binder etc. are mixed to get with organic solvent
Cathode size is coated to be obtained with drying on negative current collector, and the negative current collector is negative pole currect collecting commonly used in the art
Body, for example, copper foil or aluminium foil；Wherein described negative active core-shell material is negative active core-shell material described herein.Negative electrode active material
Proportioning between material, cathode conductive agent, negative electrode binder is known to the skilled person.
Finally, the invention provides a kind of lithium ion battery, the lithium ion battery includes housing and is contained in housing
Battery core, electrolyte, battery core include positive pole, negative pole and the barrier film between positive pole and negative pole, wherein positive pole include positive pole collection
Fluid and positive electrode, positive electrode include positive electrode active materials, positive conductive agent, positive electrode binder, and positive electrode active materials are just
Pole conductive agent, the proportioning matched somebody with somebody when each other of positive electrode binder are known to the skilled person；The preparation method of positive pole
For the preparation method of the conventional positive pole in this area, including by positive electrode active materials, positive electrode binder, positive conductive agent with it is organic molten
Agent is mixed to get anode sizing agent, and anode sizing agent is coated on into drying in plus plate current-collecting body obtains；Plus plate current-collecting body is that this area is normal
Advise the positive pole pole collector used, for example, copper foil or aluminium foil.
Due to the preparation technology of negative plate, positive plate, barrier film technology well known in the art, and the assembling of battery is also
Technology known in the field, is just repeated no more herein.
Below in conjunction with specific embodiment is to lithium ion battery anode active material of the present invention and preparation method thereof and contains
The lithium ion battery of the lithium ion battery anode active material is described further.It should be appreciated that specific reality described herein
Example is applied only to explain the present invention, is not intended to limit the present invention.Raw material passes through business employed in embodiment and comparative example
Buy.
Embodiment 1
Step 1, selection particle diameter carry out ball milling for 30nm nano-silicon and pitch（Ball-milling technology enters in a nitrogen atmosphere in experiment
OK, specified otherwise is not done subsequently）Scattered, the mass ratio of nano-silicon and pitch is 1：4, Ball-milling Time 2h, rotational speed of ball-mill 250r/
min.In a nitrogen atmosphere, heated up with 5 DEG C/min, 500 DEG C of roasting 4h.Through 210r/min, 1h ball mill grindings.Silicon-carbon is obtained to answer
The particle diameter for closing particle is 0.1 μm, labeled as A1.
Step 2, pitch is heated to 100 DEG C pitch is converted into liquid condition, add A1, the mass ratio of A1 and pitch is
1：3, through mediating stirring 1h at 100 DEG C.Take out after cooling, size-reduced machine, which is crushed, is labeled as B1.
Step 3, B1 and particle diameter for 20um natural graphite particles used into high speed mixer 300r/min, B1 and graphite
The ratio of grain is 1:25.Batch mixing 30min, makes to be uniformly distributed.It is placed in nitrogen atmosphere stove, is heated up with 5 DEG C/min, 500 DEG C of roastings
1h.Ground screening obtains final products, and the exposed surface area of the graphite particle is the 98% of graphite particle total surface area, mark
It is designated as C1.
The A1 that embodiment 1 is prepared carries out the test of Flied emission Electronic Speculum and obtains Fig. 1, as seen from Figure 1：A1 is class ball
Shape structure, centralized particle diameter is dispersed in carbon ball in 1um or so, and silicon nanoparticle, and silicon nanoparticle is equal
It is even to be dispersed in carbon ball；The test of Flied emission Electronic Speculum is carried out to the C1 prepared and obtains Fig. 2 and Fig. 3, can be seen by Fig. 2 and Fig. 3
Go out：Silicon carbide composite particles stick to the surface of graphite particle, are firmly combined with, and the surface more than 90% of graphite particle is naked state.
Embodiment 2
Step 1, selection particle diameter carry out ball milling for 30nm nano-silicon and pitch（Ball-milling technology enters in a nitrogen atmosphere in experiment
OK, specified otherwise is not done subsequently）Scattered, the mass ratio of nano-silicon and pitch is 1：2, Ball-milling Time 2h, rotational speed of ball-mill 250r/
min.In a nitrogen atmosphere, heated up with 5 DEG C/min, 500 DEG C of roasting 4h.Through 210r/min, 1h ball mill grindings.Silicon-carbon is obtained to answer
The particle diameter for closing particle is 0.5 μm, labeled as A2.
Step 2, pitch is heated to 100 DEG C pitch is converted into liquid condition, add A2, the mass ratio of A2 and pitch is
1：1, through mediating stirring 1h at 100 DEG C.Take out after cooling, size-reduced machine, which is crushed, is labeled as B2.
Step 3, B2 and particle diameter for 12um synthetic graphite particles used into high speed mixer 300r/min, B2 and graphite
The ratio of grain is 1:20.Batch mixing 30min, makes to be uniformly distributed.It is placed in nitrogen atmosphere stove, is heated up with 5 DEG C/min, 750 DEG C of roastings
1h.Ground screening obtains final products, and the exposed surface area of the graphite particle is the 85% of graphite particle total surface area, mark
It is designated as C2.
The C2 that embodiment 2 is prepared carries out Flied emission Electronic Speculum test, and test result is shown in Fig. 4 and Fig. 5, by Fig. 4 and Fig. 5
It can be seen that：Silicon nanoparticle and the formation silicon carbide composite particles particle diameter of the first organic carbon source carbonization are in 1um or so.Silicon-carbon is combined
Particle combines to form stable structure by carbon-coating with graphite particle.The surface on the surface 85% or so of graphite particle is exposed
State.
Embodiment 3
Step 1, selection particle diameter carry out ball milling for 50nm nano-silicon and pitch（Ball-milling technology enters in a nitrogen atmosphere in experiment
OK, specified otherwise is not done subsequently）Scattered, the mass ratio of nano-silicon and pitch is 0.8：1, Ball-milling Time 2h, rotational speed of ball-mill 250r/
min.In a nitrogen atmosphere, heated up with 5 DEG C/min, 800 DEG C of roasting 4h.Through 210r/min, 1h ball mill grindings.Silicon-carbon is obtained to answer
The particle diameter for closing particle is 1 μm, labeled as A3.
Step 2, pitch is heated to 150 DEG C pitch is converted into liquid condition, add A3, the mass ratio of A3 and pitch is
2：1, through mediating stirring 1h at 150 DEG C.Take out after cooling, size-reduced machine, which is crushed, is labeled as B3.
Step 3, B3 and particle diameter for 15um natural graphite particles used into high speed mixer 300r/min, B3 and graphite
The ratio of grain is 1:10.Batch mixing 30min, makes to be uniformly distributed.It is placed in nitrogen atmosphere stove, is heated up with 5 DEG C/min, 900 DEG C of roastings
1h.Ground screening obtains final products, and the exposed surface area of the graphite particle is the 85% of graphite particle total surface area, mark
It is designated as C3.
Embodiment 4
Step 1, selection particle diameter carry out ball milling for 100nm nano-silicon and pitch（Ball-milling technology is in a nitrogen atmosphere in experiment
Carry out, specified otherwise is not done subsequently）Scattered, the mass ratio of nano-silicon and pitch is 1：1, Ball-milling Time 2h, rotational speed of ball-mill 250r/
min.In a nitrogen atmosphere, heated up with 5 DEG C/min, 1000 DEG C of roasting 4h.Through 210r/min, 1h ball mill grindings.Obtain silicon-carbon
The particle diameter of composite particles is 1.5 μm, labeled as A4.
Step 2, pitch is heated to 150 DEG C pitch is converted into liquid condition, add A4, the mass ratio of A4 and pitch is
3：1, through mediating stirring 1h at 150 DEG C.Take out after cooling, size-reduced machine, which is crushed, is labeled as B4.
Step 3, B4 and particle diameter for 15um natural graphite particles used into high speed mixer 300r/min, B4 and graphite
The ratio of grain is 1:15.Batch mixing 30min, makes to be uniformly distributed.It is placed in nitrogen atmosphere stove, is heated up with 5 DEG C/min, 1000 DEG C of roastings
1h.Ground screening obtains final products, and the exposed surface area of the graphite particle is the 90% of graphite particle total surface area, mark
It is designated as C4.
Embodiment 5
Step 1, selection particle diameter carry out ball milling for 150nm nano-silicon and pitch（Ball-milling technology is in a nitrogen atmosphere in experiment
Carry out, specified otherwise is not done subsequently）Scattered, the mass ratio of nano-silicon and pitch is 1.5：1, Ball-milling Time 2h, rotational speed of ball-mill
250r/min.In a nitrogen atmosphere, heated up with 5 DEG C/min, 1000 DEG C of roasting 4h.Through 210r/min, 1h ball mill grindings.Obtain
The particle diameter of silicon carbide composite particles is 2 μm, labeled as A5.
Step 2, pitch is heated to 250 DEG C pitch is converted into liquid condition, add A5, the mass ratio of A5 and pitch is
4：1, through mediating stirring 1h at 250 DEG C.Take out after cooling, size-reduced machine, which is crushed, is labeled as B5.
Step 3, B-5 and particle diameter for 23um natural graphite particles used into high speed mixer 300r/min, B5 and graphite
The ratio of particle is 1:5.Batch mixing 30min, makes to be uniformly distributed.It is placed in nitrogen atmosphere stove, is heated up with 5 DEG C/min, 1100 DEG C of roastings
Burn 1h.Ground screening obtains final products, and the exposed surface area of the graphite particle is the 95% of graphite particle total surface area,
Labeled as C5.
Embodiment 6
Step 1, selection particle diameter carry out ball milling for 200nm nano-silicon and pitch（Ball-milling technology is in a nitrogen atmosphere in experiment
Carry out, specified otherwise is not done subsequently）Scattered, the mass ratio of nano-silicon and pitch is 2：1, Ball-milling Time 2h, rotational speed of ball-mill 250r/
min.In a nitrogen atmosphere, heated up with 5 DEG C/min, 1200 DEG C of roasting 4h.Through 210r/min, 1h ball mill grindings.Obtain silicon-carbon
The particle diameter of composite particles is 2.5 μm, labeled as A6.
Step 2, pitch is heated to 250 DEG C pitch is converted into liquid condition, add A6, the mass ratio of A6 and pitch is
5：1, through mediating stirring 1h at 250 DEG C.Take out after cooling, mark is after size-reduced machine is crushed.
Step 3, B6 and particle diameter for 25um natural graphite particles used into high speed mixer 300r/min, B6 and graphite
The ratio of grain is 1:2.Batch mixing 30min, makes to be uniformly distributed.It is placed in nitrogen atmosphere stove, is heated up with 5 DEG C/min, 1200 DEG C of roastings
1h.Ground screening obtains final products, and the exposed surface area of the graphite particle is the 80% of graphite particle total surface area, mark
It is designated as C6.
Comparative example 1
Negative active core-shell material DC1 is prepared by the method for embodiment in CN201310566652.7 3.
Performance test
1st, electron-microscope scanning is tested
Take above example 1-6 and comparative example 1 to carry out Flied emission electron-microscope scanning test, amplify 1000 times and 5000 times.To micro-
Pattern is seen to be analyzed.
2nd, the porosity of silicon carbide composite particles is measured by BET, mercury injection method.
BTE methods（Tester：N2 adsorption specific surface instrument JW-BK（The scientific and technical Co., Ltd in precise and tiny Gao Bo, Beijing）；
Method of testing:ISO-9277/GB/T19587-2004（Gas absorption BET method determines solid state material specific surface area）；
ISO-15901-2：2006/GB/T21650.2-2008（Gas adsorption method analyzes mesoporous and macropore）；ISO-15901-3/GB/-
2009（Gas absorption analyzes micropore）
The method that pore-size distribution is comparative maturity is tested with nitrogen adsorption method at present, is extensions of the determination of nitrogen adsorption BET than surface,
Utilize the Isothermal Adsorption Characteristics of nitrogen：Under liquid nitrogen temperature nitrogen in the adsorbance of the surface of solids with nitrogen relative pressure（P/
Po）And the characteristic changed, BET equations are met when P/Po is in the range of 0.05 ~ 0.35, when P/Po is more than 0.4, hair can be produced
Tubule coacervation, pore-size distribution can be determined using this characterization of adsorption.
Mercury injection method：Tester：YG-97A type high-performance mercury injection apparatuses（The scientific and technical Co., Ltd in precise and tiny Gao Bo, Beijing）
Method of testing：GB/T21650.1-2008 national standards.
3rd, exposed surface area is tested
By to the Flied emission electromicroscopic photograph under 2000 times of multiplying powers of amplification（Photo size：200mm*200mm）, it is right with gridding method
Divided in electromicroscopic photograph with the small grids of 2mm*2mm, using shared grid number as standard（Round up, less than the face of grid 50%
Product is disregarded）Silicon carbide composite particles and graphite particle whole surface area to single graphite particle surface adhesion carry out mathematical statistics meter
Calculate.30 using in electromicroscopic photograph random graphite particles collect to average and obtain graphite particle integrally exposed table as statistics total amount
Area accounts for the ratio of graphite particle total surface area.
4th, button cell is tested
Button cell is prepared as follows into sample in above example 1-6 and comparative example 1：Following methods are prepared into
Button cell：By above-described embodiment and the negative material of comparative example：Acetylene black：CMC：SBR=100：2：1.5：2.5 ratio is mixed
Uniform rear tabletting is closed, 120 DEG C of vacuum drying 24h obtain testing pole piece；Using metal lithium sheet as to electrode, celgard2400 poly- third
Alkene perforated membrane is barrier film, 1mol/L LiPF6 ethylene carbonate (EC) and the mixed solution of dimethyl carbonate (DMC)（Volume
Than for=1：1）Assembled for electrolyte in the glove box full of argon gas, prepare battery C1, C2, C3, C4, C5, C6, DC1.
Test equipment:Rechargeable battery performance detection apparatus BK-6808AR/2mA (blue odd electron Industrial Co., Ltd.).
Method of testing：5min is shelved, with the embedding lithiums of 0.1C, blanking voltage 5mv.Shelve after 10min, lithium is taken off with 0.1C, take off lithium
Blanking voltage 800mv, circulation work step is set as 50 circulations.
The first charge-discharge efficiency and removal lithium embedded of each above-mentioned battery are measured by using button cell method of testing
Removal lithium embedded capacity and capability retention after capacity, and circulation 50 times, test result is shown in Table 1.
Wherein, specific discharge capacity includes the de- lithium capacity of the embedding lithium capacity of mass ratio, mass ratio, the embedding lithium capacity of the mass ratio, matter
Amount than the computational methods of de- lithium capacity is obtained according to embedding lithium capacity and de- lithium calculation of capacity, is actual measurement removal lithium embedded capacity and pole piece
The ratio of the activity substance content of actual attachment.
Table 1
Note：First charge-discharge efficiency refers to first time charge and discharge cycles discharge capacity divided by charging capacity；Efficiency refers to discharge and recharge
Efficiency, is the percentage of de- lithium capacity and embedding lithium capacity.Capability retention refers to take off lithium specific discharge capacity and head after circulating 50 times
The percentage of secondary de- lithium specific discharge capacity.
The A1 that embodiment 1 is prepared carries out the test of Flied emission Electronic Speculum and obtains Fig. 1, as seen from Figure 1：A1 is class ball
Shape structure, centralized particle diameter is dispersed in carbon ball in 1um or so, and silicon nanoparticle, and silicon nanoparticle is equal
It is even to be dispersed in carbon ball；The test of Flied emission Electronic Speculum is carried out to the C1 prepared and obtains Fig. 2 and Fig. 3, can be seen by Fig. 2 and Fig. 3
Go out：Silicon carbide composite particles stick to the surface of graphite particle, are firmly combined with, and the surface more than 90% of graphite particle is naked state.
The C2 that embodiment 2 is prepared carries out Flied emission Electronic Speculum test, and test result is shown in Fig. 4 and Fig. 5, by Fig. 4 and Fig. 5
It can be seen that：Silicon nanoparticle and the formation silicon carbide composite particles particle diameter of the first organic carbon source carbonization are in 1um or so.Silicon-carbon is combined
Particle combines to form stable structure by carbon-coating with graphite particle.The surface on the surface 85% or so of graphite particle is exposed
State.
As shown in Table 1, embedding lithium mass ratio after battery C1, C2 that the negative material provided using the present invention is made are circulated 50 times
Capacity is up to 401.3mAh/g, 440.2 mAh/g, and it is 398.6mAh/g, 438.6 that lithium specific discharge capacity is taken off after circulating 50 times
MAh/g, capability retention highest is respectively 94.1 %, 93.5% after circulating 50 times, and cycle performance is good.
The lithium ion battery anode active material that the present invention is provided solve in the prior art lithium ion battery in discharge and recharge
During, internal layer graphite particle is with outer layer silicon carbide composite particles composite because the uneven caused outer layer silicon carbon material of expansion is opened
The problems such as splitting and come off, maintains good electrical contact, improves cycle performance of battery.
Claims (16)
1. a kind of lithium ion battery anode active material, it is characterised in that the negative active core-shell material includes graphite particle, and
The silicon carbide composite particles on graphite particle surface are dispersed in, the exposed surface area of the graphite particle is graphite particle total surface area
80%~98% 。
2. lithium ion battery anode active material according to claim 1, it is characterised in that the silicon carbide composite particles are
It is dispersed with the carbon ball of silicon nanoparticle.
3. lithium ion battery anode active material according to claim 1, it is characterised in that the graphite particle it is exposed
Surface area is the 85% ~ 90% of graphite particle total surface area.
4. lithium ion battery anode active material according to claim 1, it is characterised in that the graphite particle is averaged
Particle diameter is 10um ~ 25um.
5. lithium ion battery anode active material according to claim 4, it is characterised in that the silicon carbide composite particles
Average grain diameter is the 1% ~ 10% of graphite particle average grain diameter.
6. lithium ion battery anode active material according to claim 1, it is characterised in that the graphite particle is with disperseing
Silicon carbide composite particles number ratio on graphite particle surface is 1：1~1：100.
7. lithium ion battery anode active material according to claim 6, it is characterised in that the graphite particle is with disperseing
Number ratio is 1 between the silicon carbide composite particles on graphite particle surface：5~1：20.
8. lithium ion battery anode active material according to claim 1, it is characterised in that the silicon carbide composite particles
Porosity is 15% ~ 60%.
9. a kind of preparation method of lithium ion battery anode active material, it is characterised in that the preparation method includes：
（1）Silicon nanoparticle is mixed with the first organic carbon source, it is scattered after be carbonized obtaining silicon carbide composite particles；
（2）By step（1）In silicon carbide composite particles and the second organic carbon source it is heated mediate, obtain Surface coating second organic
The silicon carbide composite particles of carbon source；
（3）By step（2）The silicon carbide composite particles of the middle organic carbon source of Surface coating second are carbonized after being mixed with graphite particle,
Obtain negative active core-shell material.
10. preparation method according to claim 9, it is characterised in that the average grain diameter of the silicon nanoparticle be 30nm ~
200nm。
11. preparation method according to claim 9, it is characterised in that first organic carbon source and the second organic carbon source
The one kind or several being each independently selected from asphalt, coal tar pitch, sucrose, glucose, starch, phenolic resin and epoxy resin
Kind.
12. preparation method according to claim 9, it is characterised in that the step（1）Middle carburizing temperature be 500 DEG C ~
1200℃；The mass ratio of the silicon nanoparticle and the first organic carbon source is 1：5 ~ 2：1.
13. preparation method according to claim 9, it is characterised in that the step（2）Middle heating-up temperature be 100 DEG C ~
250℃；The mass ratio of the silicon carbide composite particles and the second organic carbon source is 1：3 ~ 4：1.
14. preparation method according to claim 9, it is characterised in that the step（3）Middle carburizing temperature be 750 DEG C ~
1200℃；The silicon carbide composite particles and the mass ratio of graphite particle are 1：20 ~ 1：5.
15. a kind of negative electrode of lithium ion battery, it is characterised in that the negative pole includes negative described in claim 1-8 any one
Pole active material.
16. a kind of lithium ion battery, it is characterised in that the lithium ion battery includes the negative pole described in claim 15.
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| CN112510185A (en) * | 2020-11-30 | 2021-03-16 | 南通路远科技信息有限公司 | Silicon-carbon composite negative electrode material and manufacturing method thereof |
| CN113228342A (en) * | 2020-12-28 | 2021-08-06 | 宁德新能源科技有限公司 | Negative pole piece, electrochemical device comprising same and electronic device |
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