CN110071272A - A kind of boron doping silicon substrate composite negative pole material and its preparation method and application - Google Patents
A kind of boron doping silicon substrate composite negative pole material and its preparation method and application Download PDFInfo
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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Abstract
The present invention relates to a kind of boron doping silicon substrate composite negative pole materials and its preparation method and application.The material includes the silicon oxygen carbon skeleton with rough surface, and rough surface is dispersed with four kinds of silicon covalently be combineding with each other, oxygen, carbon, boron elements.This method comprises: being freeze-dried after silicon oxygen carbon skeleton is mixed with boric acid solution, then it is pyrolyzed, is directly pyrolyzed after either mixing silicon oxygen carbon skeleton with boric acid or boron oxide.After this method boron doping, bond with carbon with surface reduces the quantity of surface carbon dangling bond, to reduce the quantity of the irreversible embedding lithium of first circle, and then improves the first circle coulombic efficiency of negative electrode material.
Description
Technical field
The invention belongs to lithium ion battery material and its preparation and application field, in particular to a kind of boron doping silicon substrate is compound
Negative electrode material and its preparation method and application.
Background technique
Silicon based anode material is with its rich reserves, environmental-friendly, electrochemical lithium storage content is high and charging/discharging voltage platform
More low advantage becomes the next-generation lithium ion battery negative material for being most hopeful to replace graphite cathode.But silicon based anode material
Very big volume change can be generated in charge and discharge process, lead to the generation of unstable SEI film, and then cycle performance is decayed
Seriously.To solve the above-mentioned problems, the nanosizing of silicon based anode material and Composite strategy are suggested, and the different silicon substrate of pattern is received
Rice cathode and composite material are prepared out.In the probe process to silicon-based active component, Si oxide is compared to elemental silicon
Partial volume expansion can be effectively inhibited, improves the cycle performance of electrode material, also, silicon is in nature mainly with oxidation
The form of state exists.Therefore, become research heat in recent years by the silicon substrate composite negative pole material of active material of silicon-base oxide
Point.
Compared with elemental silicon, Si oxide shows small volume change in cyclic process.And in first time lithiumation
The lithia and lithium metasilicate generated in situ in the process can buffer big volume change and accelerate ion transmission.But Si oxide
There is also following disadvantages: (1) the intrinsic low conductivity of Si oxide seriously reduces its chemical activity；(2) for the first time
The by-product formed in circulation consumes part lithium source, causes the initial coulombic efficiency of Si oxide relatively low.Therefore, how
It improves electric conductivity and initial coulombic efficiency is Si oxide base negative electrode material facing challenges.
In order to increase the electric conductivity of silica-base material, elemental silicon and the carbon material of good conductivity compound have as one kind
The strategy of effect.Graphene has high electric conductivity and good flexibility, while compound usually in mild item with negative electrode material
It is carried out under part, therefore is considered as most having one of highly conductive substrate of prospect for improve negative electrode material electric conductivity.Currently, passing through
Physical mixed and it is two kinds using chemical interaction building sandwich and most common prepares graphene composite material method.Most
Closely, Guo Yuguo seminar (Adv.Funct.Mater.2018,28,1705235) is by removing and restoring artificial graphite structure
For method effectively by a large amount of SiOx particulate load between the lamella inside graphite, the graphite for being prepared for high SiOx content is compound
Object.Meanwhile graphene is introduced into composite inner, facilitate the defect for solving SiOx particle poorly conductive.However, this
Method be difficult to realize the evenly dispersed of nano material on the surface of graphene and prevent nano material on the surface of graphene on exposure.
Fresh, the sol-gel method of silane has proved to be building Si oxide/carbon compound cathode materials effective ways.Mai Li
Strong seminar (Energy Storage Mater.2018,13,112) passes through control by selecting the precursor of silicon and carbon meticulously
The speed of combined polymerization obtains monodispersed SiOx/C microballoon.Although the distribution of carbon is non-inside the composite negative pole material that this method obtains
Often uniformly, the stability of circulation can be maintained, still, the negative electrode material surface that this method obtains has more dangling bond, makes
It obtains and consumes more lithium ions in first circle cyclic process, cause low coulombic efficiency.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of boron doping silicon substrate composite negative pole materials and preparation method thereof
And application, to overcome defect of the lithium ion battery negative material surface with more dangling bond in the prior art.
The present invention provides a kind of boron doping silicon substrate composite negative pole material, the material includes the silicon oxygen with rough surface
Carbon skeleton, the rough surface are dispersed with four kinds of silicon covalently be combineding with each other, oxygen, carbon, boron elements.
The boron element forms different bonding structures from carbon and oxygen with various compound states.
The silicon oxygen carbon skeleton is spheric granules.
The silicon oxygen carbon skeleton has mesopore orbit, is uniformly dispersed silicon oxygen bond in carbon-carbon bond network inside carbon skeleton.
The rough surface is by obtaining after incorporation boron to the rearrangement of surface topography.
The rearrangement of the surface topography refers to that surface forms numerous tiny particles；The tiny numbers of particles and ruler
Very little related with the doping of boron or pyrolysis temperature, i.e. the degree of roughness to pyrolysis temperature on surface and the concentration of boric acid is related.
The present invention also provides a kind of preparation methods of boron doping silicon substrate composite negative pole material, comprising:
It is freeze-dried after silicon oxygen carbon skeleton is mixed with boric acid solution with mass ratio for 1:2~1:0.05, is then pyrolyzed, or
Person is directly pyrolyzed after mixing silicon oxygen carbon skeleton for 1:2~1:0.05 with mass ratio with boric acid or boron oxide, obtains boron doping
Silicon substrate composite negative pole material；Wherein carbon skeleton has mesopore orbit, is uniformly dispersed silicon in carbon-carbon bond network inside carbon skeleton
Oxygen key.
The silicon oxygen carbon skeleton is to be carbonized by mesoporous nano organosilicon or silane (such as: ethyl orthosilicate) and carbon source
(such as: phenolic aldehyde) it is obtained by sol-gel method.
The preparation method of the mesoporous nano organosilicon includes: that ethyl alcohol is added in surfactant to mix with deionized water
In alkaline solution, organosilane precursor is added after stirring, continues to be stirred overnight to obtain evenly dispersed suspension, is centrifugated,
Drying to get, wherein the molar ratio of surfactant and deionized water be 1:10000~1:1000, organosilane precursor with go
The molar ratio of ionized water is 1:13000~1:500.
The surfactant includes cetyl trimethylammonium bromide.
The organosilane precursor is the organosilicon containing double triethoxysilicane alkyl.
The organosilane precursor includes the organosilicon containing alkyl chain, unsaturated group or aromatic group.
The alkaline solution neutral and alkali solvent that the ethyl alcohol is mixed with deionized water is ammonium hydroxide, the volume of ethyl alcohol and deionized water
Than for 1:3~1:2, the volume ratio of ammonium hydroxide and deionized water is 1:140~1:50.
The mixing time is 1-3h.
The stirring and continuation whipping temp are 25-60 degree, and revolving speed is 300-500 revs/min.
The centrifugal rotational speed is 6000-15000 revs/min；It is successively washed with ethyl alcohol and deionized water after centrifuge separation.
The technological parameter of the charing are as follows: in inert atmosphere or H2In/Ar mixed atmosphere, with 1-5 degrees/min of heating rate
It is warming up to 400~800 degree of heat preservation 6-12h.
The mixing is to utilize ultrasonic mixing.
The technological parameter of the pyrolysis are as follows: in H2In/Ar mixed atmosphere, 800 are warming up to 5-12 degrees/min of heating rate
~1000 degree of heat preservation 1-5h.
The boric acid solution concentration is 0.005-1M.
The present invention also provides a kind of application of boron doping silicon substrate composite negative pole material in lithium ion battery.
Beneficial effect
(1) organic group of intermediary hole organosilicon material of the present invention is many kinds of, can select different type according to demand
Organic group, it is hereby achieved that with different carbon contents silicon substrate composite negative pole material.Select aromatic carbon source in charcoal
The available higher carbon skeleton of degree of graphitization, is conducive to electron-transport after change.
(2) doping of boron can regulate and control the degree of roughness of surface topography in the present invention, to be conducive to ion and electronics
Transmission.The incorporation of boron while the chemical composition and structure for having regulated and controled negative electrode material surface, the chemical bonding mode pair after adulterating
Ion and electronics have stronger adsorption energy, are conducive to the promotion of high rate performance.
(3) in the present invention after boron doping, the bond with carbon with surface reduces the quantity of surface carbon dangling bond, to reduce
The quantity of the irreversible embedding lithium of first circle, and then improve the first circle coulombic efficiency of negative electrode material.
(4) the coarse surface of the present invention facilitates the quick insertion and abjection of lithium ion, so that the cathode material after doping
The features such as material has cubical expansivity low, good electrochemical cycle stability.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of boron doping silicon substrate composite negative pole material of the invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of the boron doping silicon substrate composite negative pole material of the embodiment of the present invention 1.
Fig. 3 is the x-ray diffraction pattern of the boron doping silicon substrate composite negative pole material of the embodiment of the present invention 1.
Fig. 4 is the first charge-discharge curve graph of the boron doping silicon substrate composite negative pole material of the embodiment of the present invention 1.
The multiplying power and following under high current density that Fig. 5 is the boron doping silicon substrate composite negative pole material of the embodiment of the present invention 3
Ring figure.
Fig. 6 is that the boron doping silicon substrate composite negative pole material of the embodiment of the present invention 3 is assembled into before electrode recycles later and follows
Thickness change figure after the circle of ring 500.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Main agents source: ethyl alcohol, concentrated ammonia liquor and TEOS pick up from Chinese medicines group, and BTEB, BTEE and boric acid pick up from Sigma-
Aldrich。
Temperature in the present invention is unless otherwise specified degree Celsius.
Embodiment 1
A kind of boron doping silicon substrate composite negative pole material of the present embodiment, as shown in Figure 1, being the ball with certain rough surface
Shape particle, rough surface are dispersed with four kinds of silicon, oxygen, carbon, boron elements, are be combined with each other in a manner of covalent bond.
The boron doping silicon substrate composite negative pole material of the present embodiment the preparation method comprises the following steps:
Mesoporous organosilicon nano particle is prepared, by 280mL deionized water, 120mL ethyl alcohol is added after the mixing of 2mL concentrated ammonia liquor
600mg CTAB stirs 1h, wherein and for mechanical stirring revolving speed at 400 revs/min, temperature selects 25 degree, and 0.5mL1 is then added,
Bis- (triethoxysilicane alkyl) benzene (BTEB) of 4-, are stirred overnight, obtain evenly dispersed suspension, centrifuge separation, centrifugal basket
8000 revs/min of speed selection, then successively washed each three times with ethyl alcohol and deionized water, baking oven drying is placed, particle size range is obtained
In the order mesoporous organosilicon powder of 100-200nm.
Gained white mesoporous organosilicon powder is placed in tube furnace and is carbonized, with 3 degree mins under nitrogen atmosphere protection
The heating rate of clock rises to 750 degree, natural cooling after being kept for 6 hours.Gained carbonizing production is black powder, for mesoporous hole
The carbon skeleton in road, evenly dispersed silicon oxygen bond in carbon-carbon bond network inside carbon skeleton.
The above-mentioned black powder for weighing 100mg carries out ultrasonic disperse 30 minutes with 0.06M boric acid 40mL, and then freezing is dry
It is dry.Powder after freeze-drying, which continues to be placed in tube furnace, to be pyrolyzed, in H2With 10 degrees/min of heating speed under/Ar gaseous mixture
Rate rises to 950 degree, natural cooling after being kept for 2 hours, products therefrom negative electrode material.
Gained negative electrode material is prepared into negative electrode tab by the following method: using product obtained as nano-silicone wire/carbon negative electrode active material
Matter, Super-P carbon black are conductive agent, and CMC is binder, and 8:1:1 in mass ratio is solvent tune with deionized water after mixing
Slurry is made slurry in planetary deaeration agitating device, then is coated slurry on copper foil with automatic smearing machine, and coating thickness is 7.5 μ
Then electrode is placed on the dry 12h of 80 DEG C of vacuum drying ovens by m, then negative electrode tab is cut into the size of needs with electrode preparing device.
Battery preparation: the button-shaped half-cell of LIR2032 using lithium piece be used as to electrode, in glove box according to negative electrode casing,
Electrode slice, diaphragm, lithium piece, stainless steel gasket, spring leaf, anode cover sequence assemble button cell.Electrolyte be adopted as dissolved with
Ethylene carbonate (ethylene carbonate, EC)/dimethyl carbonate (dimethylcarbonate, DMC)/5wt% fluoro
Diethyl carbonate (the diethyl of ethylene carbonate (fluoroethylene carbonate, FEC) additive modification
Carbonate, DEC) (volume ratio 3:4:3) solution 1M LiPF6。
Battery testing: new prestige battery test system is used.
Fig. 2 shows: spheric granules surface is uniformly distributed numerous little particles, so that spheric granules becomes rough, particle
It is closely coupled between particle, the bulk density of material entirety can be improved.
Fig. 3 shows: boric acid is successfully coated on original particle surface after freeze-drying, after Overheating Treatment, boric acid point
Solution is unbodied boron oxide, and boron oxide is incorporated into original SiOC ball particle surface, causes the roughening transition of surface topography.
In addition, having a small peak near 42 degree, which shows that the incorporation of boron improves degree of graphitization, is conducive to the transmission of electronics.
Fig. 4 shows: the charging platform of first lap is near 0.2V, the exactly feature charging platform of silicium cathode.
Embodiment 2
A kind of boron doping silicon substrate composite negative pole material of the present embodiment, as shown in Figure 1, being the ball with certain rough surface
Shape particle, rough surface are dispersed with four kinds of silicon, oxygen, carbon, boron elements, are be combined with each other in a manner of covalent bond.
The high performance silicon of the present embodiment/carbon nano composite anode material the preparation method comprises the following steps:
Mesoporous organosilicon nano particle is prepared referring to embodiment 1, " bis- (three ethoxies of 0.5mL Isosorbide-5-Nitrae-will be added in embodiment 1
Base silane base) benzene (BTEB) " be changed to " be added 1mL 1, bis- (triethoxysilicane alkyl) ethane (BTEE) of 2- ", remaining with implementation
Example 1 is identical, obtains particle size range in the order mesoporous organosilicon powder of 100-200nm.
Negative electrode material is prepared referring to embodiment 1, wherein boric acid solution concentration is 0.01M, volume 20mL, and pyrolysis temperature is
850 degree are risen to, remaining is same as Example 1, obtains negative electrode material.
Electrode preparation and battery assembly use method same as Example 1, repeat no more.
Embodiment 3
A kind of boron doping silicon substrate composite negative pole material of the present embodiment, as shown in Figure 1, being the ball with certain rough surface
Shape particle, rough surface are dispersed with four kinds of silicon, oxygen, carbon, boron elements, are be combined with each other in a manner of covalent bond.
The high performance silicon of the present embodiment/carbon nano composite anode material preparation method is referring to embodiment 1, and wherein boric acid is dense
Degree is 0.03M, and volume 20mL, pyrolysis temperature is to rise to 900 degree, remaining is same as Example 1, obtains negative electrode material.
Electrode preparation and battery assembly use method same as Example 1, repeat no more.
Fig. 5 shows: the electrode material shows preferable high rate performance, under the current density of 0.1A/g, reversible capacity
For 1575mAh/g, when current density increases to 2A/g, reversible capacity is still to have after 500 circles recycle up to 670mAh/g
The reversible capacity of 585mAh/g, individual pen capacity attenuation are only 0.02%.
Fig. 6 shows: after there is the electrode material 1.8 μm of applied thickness, circulation 500 to enclose in circulating ring, with a thickness of 3.0
μm, cubical expansivity is about 60%, much smaller than 300% cubical expansivity of simple substance silicon materials.
Embodiment 4
A kind of boron doping silicon substrate composite negative pole material of the present embodiment, as shown in Figure 1, being the ball with certain rough surface
Shape particle, rough surface are dispersed with four kinds of silicon, oxygen, carbon, boron elements, are be combined with each other in a manner of covalent bond.
The high performance silicon of the present embodiment/carbon nano composite anode material preparation method is referring to embodiment 1, wherein directly will
40mg boric acid is pyrolyzed after being mixed with silicon oxygen carbon skeleton, and pyrolysis temperature is to rise to 900 degree, remaining is same as Example 1, obtains
To negative electrode material.
Electrode preparation and battery assembly use method same as Example 1, repeat no more.
Comparative example 1
According to the method for embodiment 1, boric acid is not added, remaining is same as Example 1, obtains negative electrode material, repeats no more.
Comparative example 2
According to the method for embodiment 1, the precursor B TEB in the step of preparing mesoporous organosilicon is changed to positive silicic acid tetrem
Ester, remaining is same as Example 1, obtains negative electrode material, repeats no more.
Chemical property (the wherein reversible appearance for the first time of the negative electrode material of 1-4 of the embodiment of the present invention and comparative example 1-2 preparation
Amount is obtained under the current density of 0.1A/g, is obtained individual pen capacity when current density increases to 2A/g after 500 circles recycle and is declined
Lapse rate) as shown in table 1:
Table 1
It can be obtained by table 1, the silicon based anode material of function admirable can be prepared in the present invention, using the negative electrode material as cathode
The battery core that active material assembles has excellent chemical property.Specifically, when not carrying out boron doping, comparative example 1
The embedding lithium capacity of first circle and first circle coulombic efficiency are all lower, and it is extremely important to illustrate that the stability of charge and discharge electric interface is played in the incorporation of boron
Effect.Reversible capacity is in 1000mAh/g or more for the first time for embodiment 3, and coulombic efficiency is 65% for the first time, after 500 circle circulations,
Under the current density of 2A/g, individual pen capacity attenuation rate is 0.02%, good cycling stability.Embodiment 1, embodiment 2 and embodiment 4
Obtained boron doping silicon based anode material also has lower capacity attenuation rate, and reversible capacity reaches Carbon anode theory for the first time
Twice or more of capacity.
Claims (10)
1. a kind of boron doping silicon substrate composite negative pole material, which is characterized in that the material includes the silicon oxygen carbon with rough surface
Skeleton, the rough surface are dispersed with four kinds of silicon covalently be combineding with each other, oxygen, carbon, boron elements.
2. material according to claim 1, which is characterized in that the silicon oxygen carbon skeleton is spheric granules；Silicon oxygen carbon skeleton tool
There is mesopore orbit, is uniformly dispersed silicon oxygen bond in carbon-carbon bond network inside carbon skeleton；Rough surface is by right after incorporation boron
The rearrangement of surface topography and obtain.
3. a kind of preparation method of boron doping silicon substrate composite negative pole material, comprising:
It is freeze-dried after silicon oxygen carbon skeleton is mixed with boric acid solution with mass ratio for 1:2~1:0.05, is then pyrolyzed, or will
Silicon oxygen carbon skeleton is directly pyrolyzed after being mixed with boric acid or boron oxide with mass ratio for 1:0.05~1:2, obtains boron doping silicon substrate
Composite negative pole material；Wherein silicon oxygen carbon skeleton has mesopore orbit, is uniformly dispersed silicon in carbon-carbon bond network inside carbon skeleton
Oxygen key.
4. method according to claim 3, which is characterized in that the silicon oxygen carbon skeleton be carbonized by mesoporous nano organosilicon or
Person's silane and carbon source are obtained by sol-gel method.
5. method according to claim 4, which is characterized in that the preparation method of the mesoporous nano organosilicon includes: by table
Face activating agent is added in the alkaline solution that ethyl alcohol is mixed with deionized water, and organosilane precursor is added after stirring, continues stirred
At night, centrifuge separation, drying is to get wherein the molar ratio of surfactant and deionized water is 1:10000~1:1000, organic
The molar ratio of silicon precursor and deionized water is 1:13000~1:500.
6. method according to claim 5, which is characterized in that the surfactant includes cetyl trimethyl bromination
Ammonium；Organosilane precursor is the organosilicon containing double triethoxysilicane alkyl.
7. method according to claim 5, which is characterized in that the alkaline solution neutral and alkali that the ethyl alcohol is mixed with deionized water
Solvent is ammonium hydroxide, and the volume ratio of ethyl alcohol and deionized water is 1:3~1:2, and the volume ratio of ammonium hydroxide and deionized water is 1:140~1:
50。
8. method according to claim 4, which is characterized in that the technological parameter of the charing are as follows: in inert atmosphere or H2/Ar
In mixed atmosphere, 400~800 degree of heat preservation 6-12h are warming up to 1-5 degrees/min of heating rate.
9. method according to claim 3, which is characterized in that the technological parameter of the pyrolysis are as follows: in H2In/Ar mixed atmosphere,
800~1000 degree of heat preservation 1-5h are warming up to 5-12 degrees/min of heating rate；Boric acid solution concentration is 0.005-1M.
10. a kind of application of material as described in claim 1 in lithium ion battery.
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Cited By (3)
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| CN110660988A (en) * | 2019-09-27 | 2020-01-07 | 东北大学 | Silicon-based Si-B anode material and synthesis method and application thereof |
| CN112768649A (en) * | 2020-12-31 | 2021-05-07 | 东华大学 | Preparation method of boron-doped silicon-carbon composite material |
| CN113517442A (en) * | 2021-06-07 | 2021-10-19 | 宁德新能源科技有限公司 | Negative electrode material, electrochemical device, and electronic device |
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