CN109786733A - A kind of lithium ion battery negative material, preparation method and lithium ion battery - Google Patents
A kind of lithium ion battery negative material, preparation method and lithium ion battery Download PDFInfo
- Publication number
- CN109786733A CN109786733A CN201910228001.4A CN201910228001A CN109786733A CN 109786733 A CN109786733 A CN 109786733A CN 201910228001 A CN201910228001 A CN 201910228001A CN 109786733 A CN109786733 A CN 109786733A
- Authority
- CN
- China
- Prior art keywords
- ball milling
- ion battery
- lithium ion
- lithium
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of lithium ion battery negative material, preparation method and lithium ion batteries, the preparation method, the following steps are included: after Si oxide and lithium carbonate are mixed, it is warming up at 550~650 DEG C and is sintered under normal pressure, after the completion of sintering, ball milling obtains lithium ion battery negative material；The Si oxide is SiOx, wherein 1≤x≤2.In low-temperature atmosphere-pressure sintering, oxide spinel lithium can be reacted with Si oxide, generate silicic acid crystalline lithium, since sintering temperature is lower, activated silica inside Si oxide will not be reacted with lithium carbonate, the loss for avoiding material activity capacity can effectively improve the coulombic efficiency for the first time of material by subsequent ball milling.In addition, being effectively saved the energy since sintering of the invention carries out under low-temperature atmosphere-pressure, equipment requirement is mitigated.
Description
Technical field
The present invention relates to technical field of lithium ion more particularly to a kind of lithium ion battery negative materials, its preparation side
Method and lithium ion battery.
Background technique
Lithium ion battery is the main energy storage mode of current electric car.Requirement with people to electric car gradually rises
Height, the energy density of lithium ion battery is also with regard to needing to further increase.The cathode material of current commercialized power lithium-ion battery
Material mainly uses graphite, but the theoretical specific capacity of graphite only has 372mAh g-1, and also it has been exhibited to the limit.Want further
Energy density is improved, the negative electrode material of more height ratio capacity must be just used.
The theoretical specific capacity of silicon is up to 3580mAh g-1, but its expansion rate in embedding lithium reaches 300%, keeps its structure tight
It destroys again or even dusting, capacity sharply declines.Si oxide has close to 2000mAh g-1Theoretical specific capacity, be it is a kind of by
The substance of silicon and the silica composition of Nano grade.Since nano-silicon is scattered among silica, embedding and removing mistake
Expansion in journey is inhibited, and cycle performance is obviously improved.But in Si oxide for the first time process of intercalation, in material two
Silica also can embedding lithium generation silicate.Since silicate is the substance that can not take off lithium, cause the lithium of insertion that cannot be deviate from,
Cause to take off the reduction of lithium capacity for the first time, i.e., coulombic efficiency reduces for the first time.
In order to improve the coulombic efficiency for the first time of Si oxide, the silica in Si oxide can be reacted in advance, it is raw
At lithium metasilicate, to obtain a kind of Si oxide compound.Currently, generating the method for Si oxide compound mainly such as patent
Si oxide is become into gas at a high temperature of using in 106356508 A of CN 108321362 A and patent CN, then is passed through containing lithium
Gas, coulombic efficiency for the first time is promoted with this.However, this method have the shortcomings that it is some inevitable.Reaction needs
(5Pa) is carried out under extremely low pressure, this will increase the complexity of device, and entire operation process is also relative complex.The silicon that gasifies aoxidizes
Object needs 1600 DEG C of temperature, and reaction temperature is higher, and the energy consumption of experiment will sharply increase.At high temperature, inside Si oxide
Activated silica also can lead to material activity capacitance loss with the reactant salt containing lithium, and coulombic efficiency is still up for improving for the first time.
It is reported further accordance with document Journa lof Power Source188 (2009) 574-577, author uses hydrogen-oxygen
Change lithium (LiOH) and Si oxide composition generation lithium metasilicate.The result shows that the cycle performance of material is improved, but library for the first time
There is no promoted for human relations efficiency.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of lithium ion battery negative material, its preparation
The coulombic efficiency for the first time of method and lithium ion battery, lithium ion battery negative material prepared by the present invention is more excellent.
The present invention provides a kind of preparation methods of lithium ion battery negative material, comprising the following steps:
It after Si oxide and lithium carbonate are mixed, is warming up at 550~650 DEG C and is sintered under normal pressure, sintering is completed
Afterwards, ball milling obtains lithium ion battery negative material；
The Si oxide is SiOx, wherein 1≤x≤2.
Preferably, the particle size of the Si oxide is 1~5 μm.
It preferably, further include that grinding is uniform after the mixing.
Preferably, the rate of the heating is 2~15 DEG C/min.
Preferably, the sintering carries out under an inert atmosphere；The time of the sintering is 2~12h.
Preferably, the molar ratio of the Si oxide and lithium carbonate is 1:0.5~1.
Preferably, the ball milling specifically:
The sintered product is mixed with ball milling pearl according to mass ratio for 1:10~20, is placed in tungsten-carbide ball grinding jar
Carry out ball milling.
Preferably, the condition of ball milling are as follows:
Ball milling carries out under an inert atmosphere；
The revolving speed of ball milling is 500~1200r/min；
Ball milling is intermittent ball milling；In ball milling, stop 2min after every 15min；The total time of intermittent ball milling be 15~
30h。
The present invention provides a kind of lithium ion battery negative materials of preparation method preparation described above.
The present invention also provides a kind of lithium ion battery, including anode, cathode, diaphragm and electrolyte, the cathode includes
Lithium ion battery negative material described above.
The present invention provides a kind of preparation methods of lithium ion battery negative material, comprising the following steps: by Si oxide
After lithium carbonate mixing, it is warming up at 550~650 DEG C and is sintered under normal pressure, after the completion of sintering, ball milling obtains lithium-ion electric
Pond negative electrode material；The Si oxide is SiOx, wherein 1≤x≤2.In low-temperature atmosphere-pressure sintering, oxide spinel lithium can be with
Si oxide reaction, generates silicic acid crystalline lithium, since sintering temperature is lower, the activated silica inside Si oxide will not be with lithium carbonate
Reaction, avoids the loss of material activity capacity, can effectively improve the coulombic efficiency for the first time of material by subsequent ball milling.Separately
Outside, it is carried out under low-temperature atmosphere-pressure due to sintering of the invention, is effectively saved the energy, equipment requirement is mitigated.
The experimental results showed that lithium ion battery provided by the invention, under 0.05C multiplying power, embedding lithium capacity is not less than for the first time
1223mAh/g takes off lithium capacity for the first time and is not less than 878mAh/g, and coulombic efficiency is not less than 62% for the first time.
Detailed description of the invention
Fig. 1 is 1 Si oxide SiO of embodimentxXRD spectrum, after the XRD spectrum of sintered product and ball milling
The XRD spectrum of the lithium ion battery negative material arrived；
Fig. 2 is the SEM figure for the lithium ion battery negative material that embodiment 1 obtains；
Fig. 3 is the chemical property figure of experimental cell, control cell 1 and control cell 2 in embodiment 1；
Fig. 4 is the differential capacity curve of experimental cell and control cell 1 in embodiment 1.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Every other embodiment obtained by those of ordinary skill in the art without making creative efforts, belongs to this hair
The range of bright protection.
The present invention provides a kind of preparation methods of lithium ion battery negative material, comprising the following steps:
It after Si oxide and lithium carbonate are mixed, is warming up at 550~650 DEG C and is sintered under normal pressure, sintering is completed
Afterwards, ball milling obtains lithium ion battery negative material；
The Si oxide is SiOx, wherein 1≤x≤2.
The present invention first mixes Si oxide and lithium carbonate.In an embodiment of the present invention, the particle of the Si oxide
Having a size of 1~5 μm.The lithium carbonate can be carbonic acid crystalline lithium either lithium carbonate powder, and the present invention is to the lithium carbonate
Particle size has no special limitation.
In certain embodiments of the present invention, the molar ratio of the Si oxide and lithium carbonate is 1:0.5~1.Certain
In embodiment, the molar ratio of the Si oxide and lithium carbonate is 1:1 or 1:0.5.
After Si oxide and lithium carbonate are mixed, obtained mixture, which is warming up under normal pressure at 550~650 DEG C, to be burnt
Knot.
It in certain embodiments of the present invention, further include that the mixture that will be obtained is ground after Si oxide and lithium carbonate mix
Mill is uniform.The present invention has no special limitation to the method for the grinding, can grind uniformly.In certain realities of the invention
It applies in example, the obtained mixture is placed in alumina crucible, then alumina crucible is placed in tube furnace and is sintered.
In the present invention, the temperature after the heating is the temperature being sintered, and is 550~650 DEG C.In some embodiments
In, the temperature of the sintering is 580 DEG C, 600 DEG C or 620 DEG C.
In an embodiment of the present invention, the rate of the heating is 2~15 DEG C/min.In certain embodiments of the present invention
In, the rate of the heating is 5 DEG C/min, 10 DEG C/min or 8 DEG C/min.
In an embodiment of the present invention, the time of the sintering is 2~12h.In certain embodiments, the sintering when
Between be 4h, 8h or 6h.
In the present invention, the sintering carries out under normal pressure.
In an embodiment of the present invention, the sintering carries out under an inert atmosphere.In certain embodiments of the present invention, institute
Stating inert atmosphere is argon atmosphere or nitrogen atmosphere.
In low-temperature atmosphere-pressure sintering, raw material weak base lithium carbonate can be reacted with Si oxide, generate silicic acid crystalline lithium, due to
Sintering temperature is lower, and the activated silica inside Si oxide will not be reacted with lithium carbonate, avoids the loss of material activity capacity.
After the completion of sintering, sintered product ball milling is obtained into lithium ion battery negative material.
In an embodiment of the present invention, the ball milling specifically:
The sintered product is mixed with ball milling pearl according to mass ratio for 1:10~20, is placed in tungsten-carbide ball grinding jar
Carry out ball milling.
In certain embodiments of the present invention, the sintered product is that 1:20 is mixed according to mass ratio with ball milling pearl.
In certain embodiments of the present invention, the ball milling pearl is the ball milling pearl of high-energy ball milling, is specifically as follows tungsten carbide pearl.This hair
The bright size to the ball milling pearl has no special limitation, using the size of ball milling pearl well known to those skilled in the art.
In certain embodiments, the ball milling carries out in tungsten-carbide ball grinding jar.
In certain embodiments of the present invention, the ball milling carries out under an inert atmosphere.In certain embodiments, described lazy
Property atmosphere be argon atmosphere.
In certain embodiments of the present invention, the revolving speed of the ball milling is 500~1200r/min.In certain embodiments,
The revolving speed of the ball milling is 1000r/min, 800r/min or 500r/min.
In certain embodiments of the present invention, the ball milling is that intermittent ball milling stops after every 15min in ball milling
2min.The total time of the intermittence ball milling is 15~30h.In certain embodiments, the total time of the intermittent ball milling is
For 24 hours, 30h or 15h.
In the present invention, ball milling can effectively improve the coulombic efficiency for the first time of sintered product.
In certain embodiments of the present invention, the particle size of the lithium ion battery negative material is 1~4 μm.
The present invention also provides a kind of lithium ion battery negative materials of preparation method preparation described above.The present invention provides
Lithium ion battery negative material coulombic efficiency for the first time it is more excellent.In certain embodiments of the present invention, the lithium ion battery
The particle size of negative electrode material is 1~4 μm.
The present invention also provides a kind of lithium ion battery, including anode, cathode, diaphragm and electrolyte, the cathode includes
Lithium ion battery negative material described above.
The present invention does not have special limitation to the type of the anode, diaphragm and electrolyte, and e.g., lithium can be used in the anode
Piece；Porous polypropylene film can be used in the diaphragm；Ethylene carbonate (EC) and diethyl carbonate (DEC) can be used in the electrolyte
Mixed liquor.Specifically, the present invention is by lithium ion battery negative material described above, carbon black, sodium carboxymethylcellulose (CMC)
It is mixed with butadiene-styrene rubber (SBR) according to the mass ratio of 80:10:3:7, suitable quantity of water is added as dispersing agent and is tuned into slurry, so
After be coated uniformly on copper foil, and vacuum dried, roll-in is prepared into negative electrode tab；Using metal lithium sheet as positive plate, 1mol/L's
LiPF6Mixed solvent (EC: DEC=1:1 volume ratio) be electrolyte, porous polypropylene film (Celgard2300) be diaphragm,
Button cell is assembled into the glove box of argon gas protection.
The present invention carries out constant current charge-discharge experiment using the multiplying power of 0.05C, tests the cycle performance of the lithium ion battery,
Charging/discharging voltage is limited in 0.005~1.5 volt.Using the chemical property of blue electric tester (2100A) test battery, test-strips
Part is room temperature.The experimental results showed that lithium ion battery provided by the invention, under 0.05C multiplying power, embedding lithium capacity is not less than for the first time
1223mAh/g takes off lithium capacity for the first time and is not less than 878mAh/g, and coulombic efficiency is not less than 62% for the first time.
The present invention has no special limitation to the source of the raw material used above, can be general commercially available.
The present invention provides a kind of preparation methods of lithium ion battery negative material, comprising the following steps: by Si oxide
After lithium carbonate mixing, it is warming up at 550~650 DEG C and is sintered under normal pressure, after the completion of sintering, ball milling obtains lithium-ion electric
Pond negative electrode material；The Si oxide is SiOx, wherein 1≤x≤2.In low-temperature atmosphere-pressure sintering, oxide spinel lithium can be with
Si oxide reaction, generates silicic acid crystalline lithium, since sintering temperature is lower, the activated silica inside Si oxide will not be with lithium carbonate
Reaction, avoids the loss of material activity capacity, can effectively improve the coulombic efficiency for the first time of material by subsequent ball milling.Separately
Outside, it is carried out under low-temperature atmosphere-pressure due to sintering of the invention, is effectively saved the energy, equipment requirement is mitigated.
The experimental results showed that lithium ion battery provided by the invention, under 0.05C multiplying power, embedding lithium capacity is not less than for the first time
1223mAh/g takes off lithium capacity for the first time and is not less than 878mAh/g, and coulombic efficiency is not less than 62% for the first time.
In order to further illustrate the present invention, with reference to embodiments to a kind of negative electrode of lithium ion battery material provided by the invention
Material, preparation method and lithium ion battery are described in detail, but cannot be understood as limiting the scope of the present invention.
Embodiment 1
The Si oxide SiO for being 1~5 μm by 0.1mol particle sizexAfter the mixing of (1≤x≤2) and 0.1mol lithium carbonate,
Uniformly, obtained mixture is placed in alumina crucible, then is placed in tube furnace, in argon atmosphere, is heated up under normal pressure for grinding
It is sintered to 600 DEG C.The rate of heating is 5 DEG C/min, and the time of sintering is 8h.After the completion of sintering, by sintered product
It is mixed, is placed in tungsten-carbide ball grinding jar, then be brought into glove box internal lock for 1:20 according to mass ratio with tungsten carbide pearl
Firmly, guarantee to be argon atmosphere in ball grinder, obtain lithium ion battery negative material after ball milling.The revolving speed of the ball milling is 1000r/
Min, the ball milling is intermittent ball milling, in ball milling, stops 2min after every 15min, the total time of intermittent ball milling is for 24 hours.
Using X-ray diffractometer to the present embodiment Si oxide SiOx, the lithium that obtains after sintered product and ball milling
Ion battery cathode material is analyzed, and 1 Si oxide SiO of the embodiment of the present invention is obtainedxXRD spectrum, sintered product
XRD spectrum and ball milling after the obtained XRD spectrum of lithium ion battery negative material, as shown in Figure 1.Fig. 1 is embodiment 1
Si oxide SiOxXRD spectrum, the negative electrode of lithium ion battery material that obtains after the XRD spectrum of sintered product and ball milling
The XRD spectrum of material.From figure 1 it appears that original Si oxide SiOxFor amorphous state, when being sintered together with lithium carbonate
Afterwards, occurs the lithium metasilicate of crystalline state in product, by ball milling, lithium metasilicate becomes amorphous state, wherein mixed with a small amount of carbonization
Tungsten (WC) impurity.
The lithium ion battery negative material that embodiment 1 obtains is scanned electron-microscope scanning analysis by the present invention, as a result such as Fig. 2
Shown, Fig. 2 is the SEM figure for the lithium ion battery negative material that embodiment 1 obtains.From figure 2 it can be seen that gained lithium-ion electric
The particle size of pond negative electrode material is at 1~4 μm.
By the lithium ion battery negative material, carbon black, sodium carboxymethylcellulose (CMC) and butadiene-styrene rubber (SBR) according to
The mass ratio of 80:10:3:7 is mixed, and suitable quantity of water is added as dispersing agent and is tuned into slurry, is then coated uniformly on copper foil,
And vacuum dried, roll-in, it is prepared into negative electrode tab；Using metal lithium sheet as positive plate, the LiPF of 1mol/L6Mixed solvent (EC:
DEC=1:1 volume ratio) it is electrolyte, porous polypropylene film (Celgard2300) is diaphragm, in the glove box of argon gas protection
It is assembled into experimental button cell.In addition, lithium ion battery negative material is replaced with the Si oxide SiOx, obtain comparison electricity
Lithium ion battery negative material is replaced with the sintered product, obtains control cell 2 by pond 1.
The present embodiment using 0.05C multiplying power carry out constant current charge-discharge experiment, test above-mentioned lithium ion battery (including experiment
Battery, control cell 1 and control cell 2) cycle performance, charging/discharging voltage is limited in 0.005~1.5 volt.Using blue electrical measurement
The chemical property of instrument (2100A) test battery is tried, test condition is room temperature, as a result as shown in Figure 3.Fig. 3 is real in embodiment 1
The chemical property figure in electrical verification pond, control cell 1 and control cell 2.Wherein, curve 1 is the chemical property of control cell 1
Figure, curve 2 are the chemical property figure of control cell 2, and curve 3 is the chemical property figure of experimental cell.
From figure 3, it can be seen that the lithium capacity embedding for the first time of control cell 1 is 2000mAh g-1, taking off lithium capacity for the first time is
1168mAh g-1, coulombic efficiency is only 58.4% for the first time, and there is a large amount of irreversible lithiums.Control cell 2 does not have removal lithium embedded
Behavior is presented without capacity.This is because sintered lithium metasilicate is crystalline state, it is suppressed that the insertion of lithium ion leads to material
Material inactivation.And experimental cell embodies capacity, embedding lithium capacity is 1223mAh g for the first time-1, taking off lithium capacity for the first time is 888mAh g-1, and coulombic efficiency is 72.6% for the first time, coulombic efficiency is obviously more excellent for the first time.This is because Si oxide SiOxIn dioxy
SiClx and lithium carbonate reaction generates lithium metasilicate, reduce the irreversible consumption in Si oxide to lithium, make irreversible capacity from
862mAh g-1It is reduced to 335.2mAh g-1.Wherein, lithium capacity is taken off for the first time to be declined, this is because when calculating active material,
Silica has changed into lithium metasilicate, a little weight gain of material.In addition, ball milling bead mill damages generated WC impurity in mechanical milling process,
Also increase the weight of active material.
Fig. 4 is the differential capacity curve of experimental cell and control cell 1 in embodiment 1.Wherein, curve 1 is control cell 1
Differential capacity curve, curve 2 be experimental cell differential capacity curve.Figure 4, it is seen that voltage be 0.55V~
In the process of intercalation of 0.2V, control cell 1 shows a large amount of embedding lithium behavior, wherein wrapping silica containing embedding lithium and solid-state electricity
Solve the formation of matter interface (SEI)；However, the embedding lithium capacity in this section of voltage range significantly reduces, in this way for experimental cell
The consumption for just reducing irreversible lithium for the first time, makes coulombic efficiency be improved.
Embodiment 2
The Si oxide SiO for being 1~5 μm by 0.1mol particle sizexAfter the mixing of (1≤x≤2) and 0.1mol lithium carbonate,
Uniformly, obtained mixture is placed in alumina crucible, then is placed in tube furnace, in argon atmosphere, is heated up under normal pressure for grinding
It is sintered to 580 DEG C.The rate of heating is 10 DEG C/min, and the time of sintering is 4h.After the completion of sintering, by sintered product
It is mixed, is placed in tungsten-carbide ball grinding jar, then be brought into glove box internal lock for 1:20 according to mass ratio with tungsten carbide pearl
Firmly, guarantee to be argon atmosphere in ball grinder, obtain lithium ion battery negative material after ball milling.The revolving speed of the ball milling is 800r/
Min, the ball milling is intermittent ball milling, in ball milling, stops 2min after every 15min, the total time of intermittent ball milling is 30h.
By the lithium ion battery negative material, carbon black, sodium carboxymethylcellulose (CMC) and butadiene-styrene rubber (SBR) according to
The mass ratio of 80:10:3:7 is mixed, and suitable quantity of water is added as dispersing agent and is tuned into slurry, is then coated uniformly on copper foil,
And vacuum dried, roll-in, it is prepared into negative electrode tab；Using metal lithium sheet as positive plate, the LiPF of 1mol/L6Mixed solvent (EC:
DEC=1:1 volume ratio) it is electrolyte, porous polypropylene film (Celgard2300) is diaphragm, in the glove box of argon gas protection
It is assembled into experimental button cell.
The present embodiment carries out constant current charge-discharge experiment using the multiplying power of 0.05C, tests the cyclicity of above-mentioned lithium ion battery
Can, charging/discharging voltage is limited in 0.005~1.5 volt.Using the chemical property of blue electric tester (2100A) test battery, survey
Strip part is room temperature.
The experimental results showed that lithium ion battery provided in this embodiment, under 0.05C multiplying power, embedding lithium capacity is for the first time
1350mAh/g, taking off lithium capacity for the first time is 878mAh/g, and coulombic efficiency is 65% for the first time.
Embodiment 3
The Si oxide SiO for being 1~5 μm by 0.1mol particle sizexAfter the mixing of (1≤x≤2) and 0.05mol lithium carbonate,
Uniformly, obtained mixture is placed in alumina crucible, then is placed in tube furnace, in argon atmosphere, is heated up under normal pressure for grinding
It is sintered to 620 DEG C.The rate of heating is 8 DEG C/min, and the time of sintering is 6h.After the completion of sintering, by sintered product
It is mixed, is placed in tungsten-carbide ball grinding jar, then be brought into glove box internal lock for 1:20 according to mass ratio with tungsten carbide pearl
Firmly, guarantee to be argon atmosphere in ball grinder, obtain lithium ion battery negative material after ball milling.The revolving speed of the ball milling is 500r/
Min, the ball milling is intermittent ball milling, in ball milling, stops 2min after every 15min, the total time of intermittent ball milling is 15h.
By the lithium ion battery negative material, carbon black, sodium carboxymethylcellulose (CMC) and butadiene-styrene rubber (SBR) according to
The mass ratio of 80:10:3:7 is mixed, and suitable quantity of water is added as dispersing agent and is tuned into slurry, is then coated uniformly on copper foil,
And vacuum dried, roll-in, it is prepared into negative electrode tab；Using metal lithium sheet as positive plate, the LiPF of 1mol/L6Mixed solvent (EC:
DEC=1:1 volume ratio) it is electrolyte, porous polypropylene film (Celgard2300) is diaphragm, in the glove box of argon gas protection
It is assembled into experimental button cell.
The present embodiment carries out constant current charge-discharge experiment using the multiplying power of 0.05C, tests the cyclicity of the lithium ion battery
Can, charging/discharging voltage is limited in 0.005~1.5 volt.Using the chemical property of blue electric tester (2100A) test battery, survey
Strip part is room temperature.
The experimental results showed that lithium ion battery provided in this embodiment, under 0.05C multiplying power, embedding lithium capacity is for the first time
1531mAh/g, taking off lithium capacity for the first time is 949mAh/g, and coulombic efficiency is 62% for the first time.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (10)
1. a kind of preparation method of lithium ion battery negative material, comprising the following steps:
After Si oxide and lithium carbonate are mixed, it is warming up at 550~650 DEG C and is sintered under normal pressure, after the completion of sintering, ball
Mill obtains lithium ion battery negative material；
The Si oxide is SiOx, wherein 1≤x≤2.
2. preparation method according to claim 1, which is characterized in that the particle size of the Si oxide is 1~5 μm.
3. preparation method according to claim 1, which is characterized in that further include that grinding is uniform after the mixing.
4. preparation method according to claim 1, which is characterized in that the rate of the heating is 2~15 DEG C/min.
5. preparation method according to claim 1, which is characterized in that the sintering carries out under an inert atmosphere；The burning
The time of knot is 2~12h.
6. preparation method according to claim 1, which is characterized in that the molar ratio of the Si oxide and lithium carbonate is 1:
0.5~1.
7. preparation method according to claim 1, which is characterized in that the ball milling specifically:
The sintered product is mixed with ball milling pearl according to mass ratio for 1:10~20, is placed in tungsten-carbide ball grinding jar and carries out
Ball milling.
8. preparation method according to claim 7, which is characterized in that the condition of ball milling are as follows:
Ball milling carries out under an inert atmosphere；
The revolving speed of ball milling is 500~1200r/min；
Ball milling is intermittent ball milling；In ball milling, stop 2min after every 15min；The total time of intermittent ball milling is 15~30h.
9. the lithium ion battery negative material of the preparation of preparation method described in claim 1~8 any one.
10. a kind of lithium ion battery, including anode, cathode, diaphragm and electrolyte, which is characterized in that the cathode includes right
It is required that lithium ion battery negative material described in 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910228001.4A CN109786733A (en) | 2019-03-25 | 2019-03-25 | A kind of lithium ion battery negative material, preparation method and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910228001.4A CN109786733A (en) | 2019-03-25 | 2019-03-25 | A kind of lithium ion battery negative material, preparation method and lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109786733A true CN109786733A (en) | 2019-05-21 |
Family
ID=66491208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910228001.4A Pending CN109786733A (en) | 2019-03-25 | 2019-03-25 | A kind of lithium ion battery negative material, preparation method and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109786733A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111106351A (en) * | 2019-12-30 | 2020-05-05 | 深圳市研一新材料有限责任公司 | Negative electrode lithium supplement additive and preparation method thereof |
| CN111362269A (en) * | 2020-03-09 | 2020-07-03 | 上海电气集团股份有限公司 | Preparation method of SEI (solid electrolyte interphase) film of lithium ion battery cathode, lithium ion battery cathode material and application of lithium ion battery cathode material |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1407641A (en) * | 2001-09-05 | 2003-04-02 | 信越化学工业株式会社 | Monox powder containing Li and its manufacture |
| CN103151503A (en) * | 2012-12-10 | 2013-06-12 | 昆明理工大学 | Lithium ion battery silicon substrate composite negative electrode materials and preparation method thereof |
| CN103943827A (en) * | 2014-03-31 | 2014-07-23 | 华南理工大学 | High-temperature solid-phase preparation method of negative electrode material lithium orthosilicate of lithium ion battery |
| CN104022282A (en) * | 2014-05-27 | 2014-09-03 | 华南理工大学 | High temperature solid state preparation method of lithium ion battery cathode material lithium metasilicate |
| CN106356508A (en) * | 2016-09-29 | 2017-01-25 | 深圳市贝特瑞新能源材料股份有限公司 | Compound and preparation method thereof as well as negative electrode prepared by adopting compound and lithium ion battery |
| CN106654194A (en) * | 2016-11-07 | 2017-05-10 | 中国科学院化学研究所 | Element-doped SiOx negative electrode composite material as well as preparation method and application thereof |
| CN106876684A (en) * | 2017-04-12 | 2017-06-20 | 四川国创成电池材料有限公司 | A kind of lithium battery silicium cathode material, negative plate and the lithium battery prepared with it |
| CN108461723A (en) * | 2018-02-11 | 2018-08-28 | 安普瑞斯（南京）有限公司 | A kind of silicon based composite material and preparation method thereof for lithium ion battery |
-
2019
- 2019-03-25 CN CN201910228001.4A patent/CN109786733A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1407641A (en) * | 2001-09-05 | 2003-04-02 | 信越化学工业株式会社 | Monox powder containing Li and its manufacture |
| CN103151503A (en) * | 2012-12-10 | 2013-06-12 | 昆明理工大学 | Lithium ion battery silicon substrate composite negative electrode materials and preparation method thereof |
| CN103943827A (en) * | 2014-03-31 | 2014-07-23 | 华南理工大学 | High-temperature solid-phase preparation method of negative electrode material lithium orthosilicate of lithium ion battery |
| CN104022282A (en) * | 2014-05-27 | 2014-09-03 | 华南理工大学 | High temperature solid state preparation method of lithium ion battery cathode material lithium metasilicate |
| CN106356508A (en) * | 2016-09-29 | 2017-01-25 | 深圳市贝特瑞新能源材料股份有限公司 | Compound and preparation method thereof as well as negative electrode prepared by adopting compound and lithium ion battery |
| CN106654194A (en) * | 2016-11-07 | 2017-05-10 | 中国科学院化学研究所 | Element-doped SiOx negative electrode composite material as well as preparation method and application thereof |
| CN106876684A (en) * | 2017-04-12 | 2017-06-20 | 四川国创成电池材料有限公司 | A kind of lithium battery silicium cathode material, negative plate and the lithium battery prepared with it |
| CN108461723A (en) * | 2018-02-11 | 2018-08-28 | 安普瑞斯（南京）有限公司 | A kind of silicon based composite material and preparation method thereof for lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| ANGATHEVAR VELUCHAMY，ET AL.: "Improvement of cycle behaviour of SiO/C anode composite by thermochemically generated Li4SiO4 inert phase for lithium batteries", 《JOURNAL OF POWER SOURCES》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111106351A (en) * | 2019-12-30 | 2020-05-05 | 深圳市研一新材料有限责任公司 | Negative electrode lithium supplement additive and preparation method thereof |
| CN111106351B (en) * | 2019-12-30 | 2022-05-13 | 无锡零一未来新材料技术研究院有限公司 | Negative electrode lithium supplement additive and preparation method thereof |
| CN111362269A (en) * | 2020-03-09 | 2020-07-03 | 上海电气集团股份有限公司 | Preparation method of SEI (solid electrolyte interphase) film of lithium ion battery cathode, lithium ion battery cathode material and application of lithium ion battery cathode material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101767848B1 (en) | Negative electrode material for nonaqueous electrolytic secondary battery, process for producing negative electrode material for nonaqueous electrolytic secondary battery, and lithium ion secondary battery | |
| TW595036B (en) | Nanostructure lithium titanate electrode for high cycle rate rechargeable electrochemical cell | |
| JP5716093B2 (en) | Positive electrode active material for lithium ion capacitor and method for producing the same | |
| EP4092787A1 (en) | Cobalt-free layered positive electrode material and method for preparing same, and lithium-ion battery | |
| CN103943827B (en) | The high-temperature solid phase preparation method of the positive Lithium metasilicate of lithium ion battery negative material | |
| KR101886592B1 (en) | Powder for negative electrode of lithium ion secondary cell, and method for producing such powder | |
| WO2022002057A1 (en) | Silicon-oxygen composite negative electrode material, negative electrode, lithium-ion battery, and preparation methods therefor | |
| WO2022199389A1 (en) | Silicon-oxygen composite negative electrode material, preparation method therefor, and lithium ion battery | |
| CN110247033B (en) | SnS @ NSC core-double-shell cubic structure composite material and preparation method and application thereof | |
| CN113363476B (en) | Ternary cathode material of lithium ion battery and preparation method thereof | |
| CN111048770A (en) | Ternary doped silicon-based composite material and preparation method and application thereof | |
| CN105047888A (en) | Lithium ion battery anode material and preparation method thereof | |
| KR101427743B1 (en) | Metal-doped silicon oxide, anode material for secondary battery including the samme, and manufacturing method thereof | |
| CN113562714A (en) | High-compaction-density lithium iron phosphate and preparation method thereof | |
| WO2024093679A1 (en) | Positive electrode material, positive electrode sheet comprising same, and battery | |
| CN110048111A (en) | Cell positive material, battery anode slice and lithium battery | |
| KR101327681B1 (en) | Silicon oxide and anode material for lithium ion secondary cell | |
| CN107565099B (en) | Positive active material, preparation method thereof and lithium ion battery | |
| CN109786733A (en) | A kind of lithium ion battery negative material, preparation method and lithium ion battery | |
| CN107195884B (en) | A kind of lithium metasilicate doped graphene lithium ion battery negative material and preparation method thereof | |
| JP2004175609A (en) | Lithium cobaltate used for positive electrode of lithium ion battery, its manufacturing process and lithium ion battery | |
| CN114079050A (en) | Silica composite material, preparation method thereof, negative electrode material and lithium ion battery | |
| CN115020682B (en) | Preparation method of high-energy-density quick-charging graphite cathode material | |
| CN115863650A (en) | Core-shell type sodium ion battery positive electrode active material and preparation method and application thereof | |
| CN115602804A (en) | Fast ion conductor Li 2 ZrO 3 Preparation method of high-nickel-coated NCM lithium ion battery positive electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190521 |