CN109686959A - A kind of metal-modified Si oxide negative electrode material, preparation method and lithium ion battery - Google Patents
A kind of metal-modified Si oxide negative electrode material, preparation method and lithium ion battery Download PDFInfo
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Abstract
The present invention provides a kind of metal-modified Si oxide negative electrode materials, by including that metal powder and Si oxide ball milling obtain；The metal powder is selected from one or more of Sn, Ge, Ni, Go and Fe；Oxygen content is 0 x≤2 < in the Si oxide SiOx.The present invention is by deepening metal powder and Si oxide high-energy ball milling the disproportionation of Si oxide by ball milling, generating more defects and channel, improve the activity of SiOx negative electrode material.Metallic particles quality is relatively soft, under the shock of brittleness SiOx and high energy ball, is cut into superfine small nanoparticle, and be uniformly compounded in SiOx body phase.Pass through metal and Li simultaneously2There are reversible transition processes by O, and Li is released, the coulombic efficiency for the first time of SiOx negative electrode material is significantly improved.Its electric conductivity is improved simultaneously, accelerates ion diffusion, and preferably alleviate the volume expansion problem of silica-base material, to promote cycle performance of battery.
Description
Technical field
The present invention relates to technical field of lithium ion, more particularly, to a kind of metal-modified Si oxide negative electrode material,
Preparation method.
Background technique
With the aggravation of fuel fossil energy crisis and Global Greenhouse Effect problem, developing new energy becomes extremely urgent
Task.The development of new energy must rely on advanced energy storage technology, and wherein lithium ion battery is because of its high-energy density, long circulating longevity
It orders and is especially protruded the advantages that high average output voltage and become focus.Especially now, consumable electronic product is more
Quickening, the booming of power vehicle industry, the rapid popularization of smart grid and the other technical field demands newly regenerated expand
It is big to wait the demand more promoted to lithium ion battery industry accelerated development.Cathode is as one of its key constituents, directly
Determine the battery performance of lithium ion battery, mainly using currently on the market is graphite negative electrodes material.However, graphite-like is negative
Two critical defects of pole: low energy densities (theoretical specific capacity 372mAhg-1) and security risk (" analysis lithium " phenomenon) enable its nothing
Method is suitable for power battery.Therefore, it is negative to replace graphite-like to find a kind of novel high-capacity, the good and macrocyclic material of safety
Pole material becomes the key that power lithium-ion battery further develops.Silicon is because of its superelevation specific capacity (theoretical value 4200mAhg-1)、
The advantages that low intercalation potential (< 0.5V) and constituent content are abundant and show one's talent.However, adjoint during silicon lithium alloyage
Huge bulk effect (> 300%), make active material dusting, electrical contact failure and new solid-phase electrolyte layer in electrode
SEI is repeatedly generated, and is eventually led to cycle performance and is failed rapidly.To improve silicium cathode bulk effect, researchers have done various change
Property.
In recent years, a kind of raw material of industry Si oxide of industrialization (SiOx, 0 X≤2 <) causes the special of people
Concern, it is most common as aoxidized sub- silicon (SiO, x ≈ 1), it is had begun at present for lithium ion battery negative material and is shown
Strong advantage.SiOx is compared with carbon graphite material, specific capacity with higher, and it is steady that good circulation is possessed compared with Si simple substance
It is qualitative.For this purpose, researchers have done a large amount of research work to Si oxide negative electrode material in recent years.
In cell operation, due to the thermodynamic (al) unstability of organic bath, make it in low potential such as cathode work
Make to decompose at current potential and form solid electrolyte interface phase (SEI) in electrode surface, the formation of this irreversible SEI disappears
The Li for having consumed electrolyte and positive electrode abjection, leads to the significantly sacrificing and low first circulation coulomb of active positive electrode material capacity
Efficiency (ICE).Compared with lithium ion embedded reactive negative electrode material (such as graphite), SEI layers of generation is for high capacity alloying
Negative electrode material (including silicon substrate, tinbase, metal oxide etc.) is then even more serious.In addition, the oxygen in SiOx is former in embedding lithium for the first time
Son also can be with the Li in electrolyte+The Li that irreversible reaction generates inertia phase occurs2O and Li4SiO4, it is exacerbated again for the first time
Irreversible capacity, final result cause SiO negative materials head to imitate low problem, to seriously constrain SiOx negative electrode material in height
Than the application in energy lithium ion battery.
The prelithiation of lithium ion battery silicon cathode material is to make up its surface to form solid electrolyte interface phase (SEI) institute
Caused by lithium lose a kind of Critical policies.Although the prelithiation technological means up to the present possessed is rich and varied, still
So have certain problems.Strapping techniques are the easiest, can control accurate prelithiation degree, but its reaction condition must be stringent
The content of oxygen and water is controlled, is relatively suitable for the application of laboratory stage and cannot achieve large-scale application.Stable lithium metal
Powder technology is also required to strict control experiment condition, it can be achieved that fairly large application, requires instrument and equipment high, and exists
Some potential safety problems, especially in the high speed mixing process of metallic lithium powder.It can be effective by addition prelithiation additive
The coulombic efficiency for the first time of SiOx negative electrode material is improved, but traditional prelithiation reagent has flammable higher, chemical stability
It is poor and the problems such as with other electrode constituent (such as electrolyte, binder and other additives) poor compatibilities, it is easy
Lead to the generation of security risk.In recent years, high stability and new high-efficiency prelithiation additive become research hotspot, however, right
It its stability and also needs further to be promoted with the compatibility of other materials, in addition, its synthesis cost still needs to further reduce.
Therefore, how to prepare by simple method while there is the SiOx negative electrode material of high first effect and good cycle with important
Meaning.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that provide a kind of metal-modified Si oxide negative electrode material,
Metal-modified Si oxide negative electrode material provided by the invention has high coulombic efficiency for the first time.
The present invention provides a kind of metal-modified Si oxide negative electrode materials, by including metal powder and Si oxide ball milling
It obtains；The metal powder is selected from one or more of Sn, Ge, Ni, Go and Fe；Oxygen content is in the Si oxide SiOx
0 x≤2 <.
The present invention provides a kind of preparation methods of metal-modified Si oxide negative electrode material, comprising:
A) by Si oxide ball milling, a nanometer Si oxide is obtained；
B) nanometer Si oxide is mixed, ball milling with metal powder, obtains the modified Si oxide of metal nanoparticle
Negative electrode material；The metal powder is selected from one or more of Sn, Ge, Ni, Go and Fe.
Preferably, the silicon oxide particles are 4~6 μm；The particle of the nanometer Si oxide is 500~700nm.
Preferably, step A) ball milling carries out under inert gas protection；The inert gas includes Ar.
Preferably, step A) ball milling is using tungsten carbide ball milling pearl；The partial size of the tungsten carbide ball milling pearl be 1~
10mm；The ratio of grinding media to material is 10~30:1；The rotational speed of ball-mill is 800~1200r/min；The Ball-milling Time be 0.5~
24h。
Preferably, step B) mass ratio of the nanometer Si oxide and metal powder is (1~2): (1~2).
Preferably, step B) ball milling carries out under inert gas protection；The inert gas includes Ar.
Preferably, step B) ball milling is using tungsten carbide ball milling pearl；The partial size of the tungsten carbide ball milling pearl is
10mm；The ratio of grinding media to material is 10~30:1；The rotational speed of ball-mill is 800~1200r/min；The Ball-milling Time be 0.5~
24h。
Preferably, step B) partial size of the metal nanoparticle is 10nm or less.
The present invention also provides a kind of lithium ion batteries, negative including metal-modified Si oxide described in above-mentioned technical proposal
The negative electrode material that preparation method described in pole material or above-mentioned technical proposal any one is prepared.
Compared with prior art, the present invention provides a kind of metal-modified Si oxide negative electrode materials, by including metal powder
End and Si oxide ball milling obtain；The metal powder is selected from one or more of Sn, Ge, Ni, Go and Fe；The silicon oxygen
Oxygen content is 0 x≤2 < in compound SiOx.The present invention is by by one or more of Sn, Ge, Ni, Go and Fe metal powder
With Si oxide high-energy ball milling, deepens the disproportionation of Si oxide by ball milling, generate more defects and channel, improve SiOx
The activity of negative electrode material.Metallic particles quality is relatively soft simultaneously, under the shock of brittleness SiOx and high energy ball, is cut into superfine
Small nanoparticle, and be uniformly compounded in SiOx body phase.Pass through nano-metal particle and Li2The reversible transition process of O, Li is given
It releases, therefore significantly improves the coulombic efficiency for the first time of SiOx negative electrode material.Simultaneously improve its electric conductivity, accelerate from
Son diffusion, and the volume expansion problem of silica-base material is preferably alleviated, to promote cycle performance of battery.
Detailed description of the invention
Fig. 1 is the XRD diffraction pattern map of Si oxide (SiOx) under the conditions of different Ball-milling Times；
Fig. 2 is the change of size figure under Si oxide (SiOx) under the conditions of different Ball-milling Times；
Fig. 3 is the XRD diffraction pattern map of different metal modified silicon oxide composite negative pole material (MSO)；
Fig. 4 is the first charge-discharge curve graph of different metal modified silicon oxide composite negative pole material (MSO)；
Fig. 5 is the cycle performance curve graph of different metal modified silicon oxide composite negative pole material (MSO)；
Fig. 6 is coulombic efficiency comparison diagram for the first time under different blanking voltages；
Fig. 7 is the consistency analysis figure of SSO coulombic efficiency numerical value for the first time under different blanking voltages；
Fig. 8 is SSO cycle performance figure under different blanking voltages；
Fig. 9 is the charge and discharge point curve for the first time of different proportion nano-silicon oxide/metal tin composite negative pole material；
Figure 10 is the cyclic curve of different proportion nano-silicon oxide/metal tin composite negative pole material.
Specific embodiment
The present invention provides a kind of metal-modified Si oxide negative electrode material, preparation method and lithium ion battery, abilities
Field technique personnel can use for reference present disclosure, be suitably modified realization of process parameters.In particular, it should be pointed out that all similar replaces
Change and change apparent to those skilled in the art, they shall fall within the protection scope of the present invention.Of the invention
Method and application are described by preferred embodiment, and related personnel can obviously not depart from the content of present invention, spirit
Methods herein and application are modified or appropriate changes and combinations in range, carry out implementation and application the technology of the present invention.
The present invention provides a kind of metal-modified Si oxide negative electrode materials, by including metal powder and Si oxide ball milling
It obtains；The metal powder is selected from one or more of Sn, Ge, Ni, Go and Fe；Oxygen content is in the Si oxide SiOx
0 x≤2 <.
Metal-modified Si oxide negative electrode material provided by the invention is by including that metal powder and Si oxide ball milling obtain；
Wherein one or more of metal powder Sn, Ge, Ni, Go and Fe；Preferably Sn or Ge；The present invention is for the metal powder
The source and purity at end are not particularly limited, well known to those skilled in the art.
Wherein, oxygen content is 0 x≤2 < in Si oxide SiOx；, the present invention selects x ≈ 1, not only guaranteed high capacity but also
It is evident that the promotion of first effect.
The silicon oxide particles are preferably 4~6 μm；More preferably 5 μm；The particle of the nanometer Si oxide is 500
~700nm.
According to the present invention, the mass ratio of the nanometer Si oxide and metal powder is preferably (1~2): (1~2)；It can be with
For 2:1,1:1 or 1:2；Most preferably 2:1.
The present invention effectively improves its coulombic efficiency for the first time by metal-modified SiOx cathode, improves its electric conductivity,
Reduce grain diameter, generate more defects, accelerates ion diffusion, and the volume expansion for preferably alleviating silica-base material is asked
Topic, to promote cycle performance of battery.
The present invention provides a kind of preparation methods of metal-modified Si oxide negative electrode material, comprising:
A) by Si oxide ball milling, a nanometer Si oxide is obtained；
B) nanometer Si oxide is mixed, ball milling with metal powder, obtains the modified Si oxide of metal nanoparticle
Negative electrode material；The metal powder is selected from one or more of Sn, Ge, Ni, Go and Fe.
The preparation method of metal-modified Si oxide negative electrode material provided by the invention obtains first by Si oxide ball milling
Nanometer Si oxide.Specifically: by Si oxide and ball milling pearl in the environment of inert gas ball milling, obtain nano-silicon oxidation
Object.
Ball milling of the present invention is high-energy ball milling；The present invention for ball milling environment without limit, those skilled in the art
It can be tungsten-carbide ball grinding jar known to member.The ball milling pearl is preferably tungsten carbide ball milling pearl.The tungsten carbide ball milling pearl
Partial size be preferably 1~10mm；More preferably 5~10mm；Most preferably 10mm.
Before ball milling of the present invention it is also preferable to include by ball milling pearl and ball grinder be first placed in 70~80 DEG C of oven dryings 12~
24h。
Ball milling of the present invention carries out under inert gas protection；The inert gas includes Ar.The ratio of grinding media to material is preferred
For 10~30:1；More preferably 20:1；The rotational speed of ball-mill is preferably 800~1200r/min；More preferably 900~1100r/
min；Most preferably 1000r/min；The Ball-milling Time is preferably 0.5~for 24 hours；More preferably 0.5~8h；Most preferably 0.5
~6h；It is the most preferably 1~5h.
The present invention reduces silicon oxide particles size to nanoscale by above-mentioned ball milling, and the reduction of particle size can increase work
Contact specific surface area during property substance deintercalation, shortens the diffusion length of lithium ion, therefore can be significantly in terms of dynamics
Promote its chemical property；
Meanwhile during HEBM, since energy is huge, Si oxide generating unit disagreement metaplasia is at nano Si and SiO2,
In addition, impact of Si oxide during HEBM due to high-energy makes SiOx layers of its surface compact to be destroyed, oxygen also can part
Missing, generating portion surface texture defect are conducive to the diffusion of lithium ion.
Further, different rotational speed of ball-mill and time directly affect the partial size and surface defect of particle, in addition, to SiOx
Disproportionation degree have a certain impact, it is contemplated that experimental cost and material property optimize, the above-mentioned optimal item of this experiment selection
Part had not only guaranteed particle scale and disproportionation degree but also minimum had changed experimental technique.
Nanometer Si oxide is mixed, ball milling with metal powder, it is negative to obtain the modified Si oxide of metal nanoparticle
Pole material.The ball milling carries out under inert gas protection；The inert gas includes Ar.
In the present invention, the metal powder is selected from one or more of Sn, Ge, Ni, Go and Fe.Preferably Sn or
Ge；The present invention is not particularly limited the source of the metal powder and purity, well known to those skilled in the art.
Wherein, oxygen content is 0 x≤2 < in Si oxide SiOx；The silicon oxide particles are preferably 4~6 μm；It is more excellent
It is selected as 5 μm；The particle of the nanometer Si oxide is 500~700nm.
According to the present invention, the mass ratio of the nanometer Si oxide and metal powder is preferably (1~2): (1~2)；It can
Think 2:1,1:1 or 1:2；Most preferably 2:1.
The present invention for ball milling environment without limit, it is well known to those skilled in the art, can be tungsten carbide
Ball grinder.The ball milling pearl is preferably tungsten carbide ball milling pearl.The partial size of the tungsten carbide ball milling pearl is preferably 10mm.
Before ball milling of the present invention it is also preferable to include by ball milling pearl and ball grinder be first placed in 70~80 DEG C of oven dryings 12~
24h。
Ball milling of the present invention carries out under inert gas protection；The inert gas includes Ar.The ratio of grinding media to material is preferred
For 10~30:1；More preferably 20:1；The rotational speed of ball-mill is preferably 800~1200r/min；More preferably 900~1100r/
min；Most preferably 1000r/min；The Ball-milling Time is preferably 0.5~for 24 hours；More preferably 0.5~8h；Most preferably 0.5
~6h；It is the most preferably 1~5h.
After ball milling, obtain it is metal-modified after composite material MSO, as Ni/SiOx (being denoted as NSO) and Sn/SiOx (is denoted as
SSO).Ultrafine nanometer metallic particles of the present invention is uniformly distributed in SiOx body phase.
According to the present invention, after ball milling, the partial size of the metal nanoparticle is 10nm or less.The hair of the present inventor's creativeness
Existing, metallic particles partial size is necessarily less than certain critical level, can just show huge activity at this time, it can by Li2O is reversible
Conversion reaction occurs.
During HEBM, sharp impacts occur the present invention for metallic particles and brittle SiOx, further reduced SiOx
Particle size, deepened the disproportionation of SiOx, and generate more defects and channel, improved the activity of SiOx negative electrode material.
Wherein, transition metal (such as: Ni, Co and Fe) is directly formed with the Si nanocluster in SiOx during HEBM
Alloying generates NiSi, Ni2Si alloy obtains a kind of Si/SiOx/NiSi/Ni2Si even composite material, the composite wood
Material shows good cyclical stability.
And then quality is relatively soft for metal Sn particle, under the shock of brittleness SiOx and high energy WC ball, is cut into superfine small
Nanoparticle (by high-resolution transmission it can be observed that the substantially partial size of Sn is less than 5nm), and uniformly it is compounded in SiOx body phase.Nanometer
The compound electric conductivity that can promote SiOx negative electrode material to a certain degree of Sn, further, since the compound of multiphase can also be further
Buffer its bulk effect.But herein most of all, metal Sn and Li2There are reversible transition processes by O:And SiOx negative electrode material is a large amount of due to generating during potentiality for the first time
Can not anti-phase Li2O, significantly reduce its coulombic efficiency for the first time, when SiOx cathode carries out de- lithium, nanometer Sn can be by SiOx
The Li generated when embedding lithium for the first time2Li in O is released, therefore significantly improves the effect of coulomb for the first time of SiOx negative electrode material
Rate.
The present invention also provides a kind of lithium ion batteries, negative including metal-modified Si oxide described in above-mentioned technical proposal
The negative electrode material that preparation method described in pole material or above-mentioned technical proposal any one is prepared.
Lithium ion battery provided by the invention, including above-mentioned negative electrode material, positive electrode, electrolyte, diaphragm material.This hair
It is bright it is above-mentioned for above-mentioned negative electrode material had clear description, details are not described herein.
The present invention for the positive electrode, electrolyte, diaphragm material without limit, it is well known to those skilled in the art
?.
It is preferred that can be with are as follows: the composite material prepared is modulated slurry in SP, CMC+SBR with 6:2:2, is coated in copper foil
On, 80 DEG C of drying, film-making simultaneously assembles button cell.
The present invention provides a kind of metal-modified Si oxide negative electrode materials, by including metal powder and Si oxide ball milling
It obtains；The metal powder is selected from one or more of Sn, Ge, Ni, Go and Fe；Oxygen content is in the Si oxide SiOx
0 x≤2 <.The present invention by by one or more of Sn, Ge, Ni, Go and Fe metal powder and Si oxide high-energy ball milling,
The disproportionation for deepening Si oxide by ball milling, generates more defects and channel, improves the activity of SiOx negative electrode material.Simultaneously
Metallic particles quality is relatively soft, under the shock of brittleness SiOx and high energy ball, is cut into superfine small nanoparticle, and uniformly multiple
It closes in SiOx body phase.Pass through metal and Li simultaneously2O is released Li there are reversible transition process, therefore significantly mentions
The coulombic efficiency for the first time of SiOx negative electrode material is risen.Its electric conductivity is improved simultaneously, accelerates ion diffusion, and preferably alleviate
The volume expansion problem of silica-base material, to promote cycle performance of battery.
In order to further illustrate the present invention, with reference to embodiments to a kind of metal-modified Si oxide provided by the invention
Negative electrode material, preparation method and lithium ion battery are described in detail.
Embodiment 1 (influence of Ball-milling Time)
SiO (5 μm), tungsten carbide ball milling pearl (10mm) and tungsten-carbide ball grinding jar are first placed in 80 DEG C of one nights of oven drying,
It is then charged with inert atmosphere (Ar), is that ball is added in 20:1 and SiO raw material, rotational speed of ball-mill 1000rpm are obtained with WC ratio of grinding media to material
Nano silicone oxide material (is denoted as nSiOx), is then modulated and is starched with 6:2:2 to the nSiOx and SP, CMC+SBR that are prepared
Material is coated on copper foil, and 80 DEG C of drying, film-making simultaneously assembles button cell.Performance measurement is carried out to it.This experimental study difference
Ball-milling Time 0.5h, 1h, 2h, 4h and for 24 hours influence to material prepared performance:
Table 1 be under the conditions of the different Ball-milling Times of the embodiment of the present invention 1 Si oxide (SiOx) first charge-discharge capacity with
Coulombic efficiency contrast table for the first time, by table 1, it can be seen that, high-energy ball milling (HEBM) can enable SiOx that a small amount of disproportionation occurs, the reason is that due to
HEBM can provide huge energy.During Ball-milling Time is from 0.5h to 2h, with the increase of Ball-milling Time, SiOx capacity is played
Higher and higher, coulombic efficiency has slight variation for the first time, the reason is that generating layer is more since ball milling is by the fine and close damage layer on the surface SiOx
More defects, while being that material is more active, therefore capacity increases, coulombic efficiency slightly decreases for the first time；When ball milling
Between more than 2h when, continue growing Ball-milling Time, SiOx capacity is without significant change.Therefore, to give full play to SiOx capacity, when ball milling
Between selection preferably >=2h.
Fig. 1 is the XRD diffraction pattern map of Si oxide (SiOx) under the conditions of the different Ball-milling Times of the embodiment of the present invention 1,
By Fig. 1, it can be seen that, high-energy ball milling (HEBM) can enable SiOx that a small amount of disproportionation occurs, the reason is that since HEBM can provide huge energy
Amount；In addition, thering is the XRD diffractive features peak of micro WC to occur, the reason is that too due to Ball-milling Time when Ball-milling Time is more than 2h
Long, mild wear occurs for WC ball milling pearl, for this purpose, to avoid WC impurity from interfering, Ball-milling Time answers≤2h.
Fig. 2 is the grain size distribution under Si oxide (SiOx) under the conditions of the different Ball-milling Times of the embodiment of the present invention 1, by scheming
It can be seen that grain diameter variation is unobvious with the increase of Ball-milling Time.
The first charge-discharge specific capacity and the variation table of coulombic efficiency for the first time of M/SiOx under the different Ball-milling Times of table 1
Embodiment 2 (different metal is modified)
SiOx (5 μm, x ≈ 1), tungsten carbide ball milling pearl (10mm) and tungsten-carbide ball grinding jar are first placed in 80 DEG C of oven dryings
One night was then charged with inert atmosphere (Ar), was that ball is added in 20:1 and SiOx raw material, Ball-milling Time 2h obtain nanometer with WC ratio of grinding media to material
Grade SiOx (being denoted as nSiOx) is then again mixed nS and metal (M) granular materials with mass ratio nSiOx/M=2/1 ratio
It is even, high-energy ball milling is carried out with above-mentioned similarity condition again, obtains the modified silicon oxide composite material MSO of metal material.It is right
The composite material being prepared modulates slurry in SP, CMC+SBR with 6:2:2, is coated on copper foil, 80 DEG C of drying, film-making and group
Button cell is filled, performance measurement is carried out to it.The modified Si oxide of this experimental study different metal material (M=Sn and Ni)
The influence of (being expressed as NSO and SSO) to material prepared performance
Fig. 3 is the XRD diffraction pattern of 2 different metal modified silicon oxide composite negative pole material (MSO) of the embodiment of the present invention
Map, it can be obtained from the figure that knowing, high-energy ball milling (HEBM) can enable SiOx that a small amount of disproportionation occurs；By the nSiOx after W metal ball milling modification
Ni-Si alloy is generated, and alloying reaction is not occurred by the modified nSiOx of metal Sn, still maintains oneself independent crystalline substance
Type.
Fig. 4 is 2 different metal modified silicon oxide composite negative pole material (MSO) of the embodiment of the present invention in 0.005V-1.5V
Between with the first charge-discharge curve comparison figure under 0.05C multiplying power.It can be obtained from the figure that, wherein there is not metal-modified nSiOx, it is first
Secondary to put/charging capacity highest, respectively 3060.6mAh/g and 1857mAh/g, coulombic efficiency is 60.67% for the first time；By metal
The modified nSiOx of Ni (NSO) its put for the first time/charging capacity is minimum, respectively 1103.5mAh/g and 639.8mAh/g, for the first time
Coulombic efficiency is not also high, is 57.98%；And higher specific capacity is then shown by the modified nSiOx of metal Sn (SSO), it is first
Secondary discharge capacity 1975.2mAh/g, initial charge capacity 1476.2mAh/g and highest coulombic efficiency 74.74% for the first time.
Fig. 5 is 2 different metal modified silicon oxide composite negative pole material (MSO) of the embodiment of the present invention in 0.005V-1.5V
Between cycle performance curve, it is preceding two circle be 0.05C low current activate, be later 0.2C circulation.Learn there is not gold by figure
The modified nanometer Si oxide (nSiOx) of category specific capacity highest in former circles circulation, but capacity attenuation is quickly, cycle performance
It is worst；Best cycle performance is shown by the modified nSiOx of W metal (NSO), still, capacity is minimum；And by metal
The modified nSiOx of Sn keeps higher specific capacity while showing excellent cycle performance.
Embodiment 3 (not influence of the charge cutoff voltage to MSO chemical property)
SiOx (5 μm, x ≈ 1), tungsten carbide ball milling pearl (10mm) and tungsten-carbide ball grinding jar are first placed in 80 DEG C of oven dryings
One night was then charged with inert atmosphere (Ar), was that ball is added in 20:1 and SiOx raw material, Ball-milling Time 2h obtain nanometer with WC ratio of grinding media to material
Grade SiOx (being denoted as nSiOx), is then again mixed nSiOx with metallic particles (Ni or Sn) with mass ratio nSiOx/M=2/1
It is even, again with above-mentioned similarity condition carry out high-energy ball milling, obtain it is metal-modified after silicon oxide composite material (NSO and SSO).
Slurry is modulated with 6:2:2 in SP, CMC+SBR to the composite material being prepared, is coated on copper foil, 80 DEG C of drying, film-making is simultaneously
Button cell is assembled, performance measurement is carried out to it.Not influence of the charge cutoff voltage to its chemical property of this experimental study.
Fig. 6 is the metal-modified Si oxide MSO composite negative pole material of the embodiment of the present invention 3 under not charge cutoff voltage
Coulombic efficiency comparison diagram for the first time.It can be obtained from the figure that know, when charge cutoff voltage is 1.5V, the library for the first time of nSiOx, NSO and SSO
Human relations efficiency is respectively 62.88%, 58.31% and 73.36%, and when charge cutoff voltage is 3V, three's coulombic efficiency for the first time
Respectively 70.91%, 78.47% and 85.38%, it is SSO highest.However three's main current potential that coulombic efficiency is promoted for the first time
Section is different, and wherein nSiOx is 0.005-1V, NSO 0.005-2.5V, SSO 0.005-2V.
Fig. 7 is modified Si oxide (SSO) composite negative pole material of 3 metal Sn of the embodiment of the present invention under different blanking voltages
The consistency of coulombic efficiency for the first time analysis chart.It is learnt by figure, all data show good consistency, and result is by gold
Belong to the modified Si oxide of Sn (SSO) in the section 1.5V and 3V, compared to without metal-modified Si oxide
(nSiOx), coulombic efficiency has the promotion of 13%-15% for the first time.
Fig. 8 is modified Si oxide (SSO) composite negative pole material of 3 metal Sn of the embodiment of the present invention under different blanking voltages
Cycle performance figure.It can be obtained from the figure that knowing, with the increase of charge cutoff voltage, cycle performance decaying is more serious.
Embodiment 4 (influence of different proportion nano-silicon oxide/metal tin, preferably nSiOx/Sn=2/1)
SiOx (5 μm, x ≈ 1), tungsten carbide ball milling pearl (10mm) and tungsten-carbide ball grinding jar are first placed in 80 DEG C of oven dryings
One night was then charged with inert atmosphere (Ar), was that ball is added in 20:1 and SiOx raw material, Ball-milling Time 2h obtain nanometer with WC ratio of grinding media to material
Grade SiOx (being denoted as nSiOx), then nSiOx is uniformly mixed with metal Sn granular materials again, again with above-mentioned similarity condition into
Row high-energy ball milling obtains the modified silicon oxide composite material MSO of metal material.To the composite material being prepared in SP,
CMC+SBR modulates slurry with 6:2:2, is coated on copper foil, and 80 DEG C of drying, film-making simultaneously assembles button cell, carries out performance to it
Measurement.This experimental study different metal material Sn and nanometer Si oxide nSiOx ratio (nSiOx/Sn=2/1,1/1 and 1/
2, it is denoted as SSO-1, SSO-2 and SSO-3 respectively) influence to material prepared performance.
Fig. 9 is that 4 different proportion nano-silicon oxide/metal tin composite negative pole material (MSO) of the embodiment of the present invention exists
With the first charge-discharge curve comparison figure under 0.05C low range between 0.05V-2.5V, it can be obtained from the figure that knowing, with metal Sn content
Increase, first charge-discharge capacity gradually decreases, and coulombic efficiency variation for the first time is little.
Figure 10 is that 4 different proportion nano-silicon oxide/metal tin composite negative pole material (MSO) of the embodiment of the present invention exists
Preceding two circle under 0.05C low range between 0.05V-1.5V to activate, later with the cyclic curve figure under 0.2C multiplying power.It can by figure
Know, with the increase of metal Sn content, capacity is gradually decreased, and cycle performance also has certain reduction.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of metal-modified Si oxide negative electrode material, by including that metal powder and Si oxide ball milling obtain；The metal
Powder is selected from one or more of Sn, Ge, Ni, Go and Fe；Oxygen content is 0 x≤2 < in the Si oxide SiOx.
2. a kind of preparation method of metal-modified Si oxide negative electrode material, comprising:
A) by Si oxide ball milling, a nanometer Si oxide is obtained；
B) nanometer Si oxide is mixed, ball milling with metal powder, obtains the modified Si oxide cathode of metal nanoparticle
Material；The metal powder is selected from one or more of Sn, Ge, Ni, Go and Fe.
3. preparation method according to claim 2, which is characterized in that the silicon oxide particles are 4~6 μm；It is described to receive
The particle of rice Si oxide is 500~700nm.
4. preparation method according to claim 2, which is characterized in that step A) ball milling under inert gas protection into
Row；The inert gas includes Ar.
5. preparation method according to claim 2, which is characterized in that step A) ball milling is using tungsten carbide ball milling
Pearl；The partial size of the tungsten carbide ball milling pearl is 1~10mm；The ratio of grinding media to material is 10~30:1；The rotational speed of ball-mill be 800~
1200r/min；The Ball-milling Time be 0.5~for 24 hours.
6. preparation method according to claim 2, which is characterized in that step B) the nanometer Si oxide and metal powder
Mass ratio be (1~2): (1~2).
7. preparation method according to claim 2, which is characterized in that step B) ball milling under inert gas protection into
Row；The inert gas includes Ar.
8. preparation method according to claim 2, which is characterized in that step B) ball milling is using tungsten carbide ball milling
Pearl；The partial size of the tungsten carbide ball milling pearl is 10mm；The ratio of grinding media to material is 10~30:1；The rotational speed of ball-mill be 800~
1200r/min；The Ball-milling Time be 0.5~for 24 hours.
9. preparation method according to claim 2, which is characterized in that step B) partial size of the metal nanoparticle is
10nm or less.
10. a kind of lithium ion battery, which is characterized in that including metal-modified Si oxide negative electrode material described in claim 1
Or the negative electrode material that preparation method described in claim 2~9 any one is prepared.
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| CN110518246A (en) * | 2019-08-12 | 2019-11-29 | 西安交通大学 | Application of the metal fluoride in lithium ion battery oxidation silicium cathode |
| CN110911643A (en) * | 2019-12-05 | 2020-03-24 | 江苏科技大学 | Diatomite-based lithium ion battery negative electrode material and preparation method thereof |
| CN110993915A (en) * | 2019-12-11 | 2020-04-10 | 江苏大学 | SiO for lithium ion batteryxPreparation method of @ M @ CNTs composite anode material |
| CN111129458A (en) * | 2019-12-20 | 2020-05-08 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of nano lithium silicide powder composite material, product and application thereof |
| CN111916705A (en) * | 2020-08-05 | 2020-11-10 | 西北师范大学 | Preparation and application of high-performance silicon oxide-based composite material |
| CN112289997A (en) * | 2020-10-30 | 2021-01-29 | 中国科学院长春应用化学研究所 | Silicon dioxide-based composite negative electrode material for lithium ion battery and preparation method thereof |
| CN112635730A (en) * | 2020-12-17 | 2021-04-09 | 华南理工大学 | Silica-based negative electrode material with high reversible capacity and preparation and application thereof |
| CN116190620A (en) * | 2023-04-25 | 2023-05-30 | 北京科技大学 | Silicon germanium oxygen composite material and preparation method and application thereof |
| CN117199327A (en) * | 2023-11-07 | 2023-12-08 | 南通大学 | Quick-charging silicon-based negative electrode material for lithium battery and preparation method thereof |
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| CN110518246A (en) * | 2019-08-12 | 2019-11-29 | 西安交通大学 | Application of the metal fluoride in lithium ion battery oxidation silicium cathode |
| CN110911643A (en) * | 2019-12-05 | 2020-03-24 | 江苏科技大学 | Diatomite-based lithium ion battery negative electrode material and preparation method thereof |
| CN110993915A (en) * | 2019-12-11 | 2020-04-10 | 江苏大学 | SiO for lithium ion batteryxPreparation method of @ M @ CNTs composite anode material |
| CN111129458A (en) * | 2019-12-20 | 2020-05-08 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of nano lithium silicide powder composite material, product and application thereof |
| CN111916705A (en) * | 2020-08-05 | 2020-11-10 | 西北师范大学 | Preparation and application of high-performance silicon oxide-based composite material |
| CN111916705B (en) * | 2020-08-05 | 2023-01-31 | 西北师范大学 | Preparation and application of high-performance silicon oxide-based composite material |
| CN112289997A (en) * | 2020-10-30 | 2021-01-29 | 中国科学院长春应用化学研究所 | Silicon dioxide-based composite negative electrode material for lithium ion battery and preparation method thereof |
| CN112635730A (en) * | 2020-12-17 | 2021-04-09 | 华南理工大学 | Silica-based negative electrode material with high reversible capacity and preparation and application thereof |
| CN116190620A (en) * | 2023-04-25 | 2023-05-30 | 北京科技大学 | Silicon germanium oxygen composite material and preparation method and application thereof |
| CN117199327A (en) * | 2023-11-07 | 2023-12-08 | 南通大学 | Quick-charging silicon-based negative electrode material for lithium battery and preparation method thereof |
| CN117199327B (en) * | 2023-11-07 | 2024-05-03 | 南通大学 | Quick-charging silicon-based negative electrode material for lithium battery and preparation method thereof |
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