CN110176592A - A kind of preparation method and applications of doped carbon/silicon composite - Google Patents
A kind of preparation method and applications of doped carbon/silicon composite Download PDFInfo
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- CN110176592A CN110176592A CN201910477171.6A CN201910477171A CN110176592A CN 110176592 A CN110176592 A CN 110176592A CN 201910477171 A CN201910477171 A CN 201910477171A CN 110176592 A CN110176592 A CN 110176592A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a kind of preparation method and applications of doped carbon/silicon composite, and described method includes following steps: (1) mixing one or more of nitrogen source, phosphorus source, sulphur source with inert gas, using the carbon material of high temperature gas phase method synthesis doping；(2) under inert atmosphere protection, carbon material will be adulterated using ball-milling method and is mixed with silicon powder, doped carbon/silicon composite is obtained.In composite material, the electric conductivity of electrode material is can be improved in the carbon material of doping, improves the electro-chemical activity of silicon materials；The carbon material of doping can serve as buffer layer, and the volume expansion problem in the charge and discharge process of silicon materials is effectively relieved, and improve battery cycle life；The carbon material of doping can provide additional electrochemical lithium storage content, improve the specific capacity of composite material.
Description
Technical field
The invention belongs to technical field of composite materials, be related to a kind of doped carbon/silicon composite preparation method and its
Application in lithium ion battery.
Background technique
Lithium ion battery is filled as the energy supply of presently the most widely used mobile electronic device and electric vehicle
It sets, since the theoretical specific capacity of commercialization graphite cathode is only 374 mAh g-1, it is difficult to meet market for high specific energy lithium ion
The demand for development of battery.The theoretical capacity of silicium cathode is up to 4200 mAh g-1, and rich reserves are environmentally friendly, by
It is considered the next-generation ideal negative electrode material of high specific energy lithium ion battery.But due to the electric conductivity and charge and discharge of the difference of silicon materials
Huge volume expansion problem in the process, so that silica-base material shows very poor cycle performance and high rate performance, it is difficult to practical
Change application.In order to solve the problems, such as poorly conductive existing for current silicon materials and volume expansion, the cycle life of battery is improved, by silicon
Material and carbon material carry out compound being a kind of effective strategy, on the one hand electrode material can be improved in the carbon material of introducing
Electric conductivity；On the other hand it can be used as buffer medium, alleviate the volume expansion problem of silicon materials charge and discharge process, promote battery
Cycle life.But since the lithium ion memory capacity of single carbon material is lower, the same of cycle performance is improved introducing carbon material
When, it will cause the decline of the specific capacity of battery entirety.
Compared with traditional single carbon material, the carbon material of nonmetal doping has higher electro-chemical activity, higher
Electrochemical lithium storage content.Therefore, silicon materials and the progress of the carbon material of doping are compound, the same of cycle performance of battery can improved
When, it ensure that the higher specific capacity of electrode material.
Summary of the invention
The object of the present invention is to provide a kind of preparation method and applications of doped carbon/silicon composite, using High Temperature Gas
The carbon material of phase method synthesis doping, recycles ball-milling method to prepare doped carbon/silicon composite, and then study its chemical property.
The result shows that carrying out the compound reversible specific capacity and cycle performance that can significantly improve silicon materials with doping carbon material.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of preparation method of doped carbon/silicon composite, includes the following steps:
(1) by one or more of nitrogen source, phosphorus source, sulphur source and inert gas (Ar or N2) mixing, using high temperature gas phase method
Synthesize the carbon material of doping；
In this step, the nitrogen source is NH3, phosphorus source PH3, sulphur source H2S；The volume fraction control of nitrogen source, phosphorus source or sulphur source exists
Between 3 ~ 15%；The carbon material is one of Ketjen black, super P, acetylene black, graphene, carbon nanotube；The high temperature
The step of carbon material of vapor phase method synthesis doping, is as follows: in tube furnace, carrying out within the temperature range of 300 ~ 700 DEG C to carbon material
Doping vario-property 2 ~ 6 hours；
(2) (Ar or N under inert atmosphere protection2), carbon material will be adulterated using ball-milling method and is mixed with silicon powder, is adulterated
Carbon/silicon composite；
In this step, between 1:1 ~ 1:9, Ball-milling Time is greater than 36 hours for doping carbon material/silicon powder mass ratio control,
Rotational speed of ball-mill is set as 400 ~ 750 r/min.
Doped carbon/silicon composite that the above method is prepared can be used as cathode and apply in lithium ion battery and solid-state electricity
Chi Zhong.
Compared with the prior art, the present invention has the advantage that
1, the electric conductivity of electrode material can be improved in the carbon material adulterated, improves the electro-chemical activity of silicon materials.
2, the carbon material adulterated can serve as buffer layer, and the volume expansion being effectively relieved in the charge and discharge process of silicon materials is asked
Topic improves battery cycle life.
3, the carbon material adulterated can provide additional electrochemical lithium storage content, improve the specific capacity of composite material.
Detailed description of the invention
Fig. 1 is carbon material/silicon composite of the different doping of embodiment 1-3 preparation in 0.5 A g-1Current density under
Cycle performance figure.
Fig. 2 is the carbon of (cathode) sulfur doping | | 0.2 A/g cycle performance figure of cobalt acid lithium (anode) full battery.
Specific embodiment
Below with reference to embodiment, further description of the technical solution of the present invention, and however, it is not limited to this, all right
Technical solution of the present invention is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be contained
Lid is within the protection scope of the present invention.
Embodiment 1
Carbon/silicon composite of N doping is prepared according to the following steps in the present embodiment:
(1) NH3Under/Ar mixed atmosphere, NH3Volume fraction control is 3%, and Ketjen black quality is 500 mg, with the liter of 5 DEG C/min
Warm rate keeps the temperature 2 hours at 300 DEG C, obtains the carbon material of N doping.
(2) by the carbon material of obtained N doping and nano silica fume in N2Ball milling mixing is carried out under atmosphere, rotational speed of ball-mill is
400 r/min, Ball-milling Time are 36 hours.The carbon of N doping/silicon powder mass ratio is 1:1, obtains carbon/silicon composite wood of N doping
Material.
Chemical property figure of the carbon/silicon composite of sulfur doping manufactured in the present embodiment in lithium ion full battery is as schemed
Shown in 2.
Embodiment 2
Carbon/silicon composite of phosphorus doping is prepared according to the following steps in the present embodiment:
(1) PH3Under/Ar mixed atmosphere, PH3Volume fraction control is 3%, and Ketjen black quality is 500 mg, with the liter of 5 DEG C/min
Warm rate keeps the temperature 2 hours at 300 DEG C, obtains the carbon material of phosphorus doping.
(2) by the carbon material of obtained phosphorus doping and nano silica fume in N2Ball milling mixing is carried out under atmosphere, rotational speed of ball-mill is
400 r/min, Ball-milling Time are 36 hours.The carbon of phosphorus doping/silicon powder mass ratio is 1:1, obtains carbon/silicon composite wood of phosphorus doping
Material.
Embodiment 3
Carbon/silicon composite of sulfur doping is prepared according to the following steps in the present embodiment:
(1) H2Under S/Ar mixed atmosphere, H2The control of S volume fraction is 3%, and Ketjen black quality is 500 mg, with the liter of 5 DEG C/min
Warm rate keeps the temperature 2 hours at 300 DEG C, obtains the carbon material of sulfur doping.
(2) by the carbon material of obtained sulfur doping and nano silica fume in N2Ball milling mixing is carried out under atmosphere, rotational speed of ball-mill is
400 r/min, Ball-milling Time are 36 hours.The carbon of sulfur doping/silicon powder mass ratio is 1:1, obtains carbon/silicon composite wood of sulfur doping
Material.
By the embodiment 1-3 doped carbon/silicon composite prepared and conductive agent, binder is mixed according to certain mass ratio
It stirs evenly, coating on a current collector, is prepared into electrode, studies its chemical property, in 0.5 A g-1Current density under
Cycle performance it is as shown in Figure 1.As shown in Figure 1, after the compound silicon cycling 50 of sulphur/phosphorus/N doping carbon encloses, specific discharge capacity
Respectively 610,505,290 mAh/g, and individually silicon powder specific capacity is only 97 mAh/g.It can be concluded that the introducing of the carbon of doping
The chemical property of silicium cathode is obviously improved.
Embodiment 4
Carbon/silicon composite of N doping is prepared according to the following steps in the present embodiment:
(1) NH3Under/Ar mixed atmosphere, NH3Volume fraction control is 15%, and Ketjen black quality is 500 mg, with the liter of 5 DEG C/min
Warm rate keeps the temperature 2 hours at 300 DEG C, obtains the carbon material of N doping.
(2) by the carbon material of obtained N doping and nano silica fume in N2Ball milling mixing is carried out under atmosphere, rotational speed of ball-mill is
400 r/min, Ball-milling Time are 36 hours.The carbon of N doping/silicon powder mass ratio is 1:1, obtains carbon/silicon composite wood of N doping
Material.
Embodiment 5
Carbon/silicon composite of N doping is prepared according to the following steps in the present embodiment:
(1) NH3Under/Ar mixed atmosphere, NH3Volume fraction control is 3%, and Ketjen black quality is 500 mg, with the liter of 5 DEG C/min
Warm rate keeps the temperature 2 hours at 700 DEG C, obtains the carbon material of N doping.
(2) by the carbon material of obtained N doping and nano silica fume in N2Ball milling mixing is carried out under atmosphere, rotational speed of ball-mill is
400 r/min, Ball-milling Time are 36 hours.The carbon of N doping/silicon powder mass ratio is 1:1, obtains carbon/silicon composite wood of N doping
Material.
Embodiment 6
Carbon/silicon composite of N doping is prepared according to the following steps in the present embodiment:
(1) NH3Under/Ar mixed atmosphere, NH3Volume fraction control is 3%, and Ketjen black quality is 500 mg, with the liter of 5 DEG C/min
Warm rate keeps the temperature 2 hours at 300 DEG C, obtains the carbon material of N doping.
(2) by the carbon material of obtained N doping and nano silica fume in N2Ball milling mixing is carried out under atmosphere, rotational speed of ball-mill is
400 r/min, Ball-milling Time are 36 hours.The carbon of N doping/silicon powder mass ratio is 1:9, obtains carbon/silicon composite wood of N doping
Material.
Claims (9)
1. a kind of preparation method of doped carbon/silicon composite, spy are that described method includes following steps:
(1) one or more of nitrogen source, phosphorus source, sulphur source are mixed with inert gas, is synthesized and is adulterated using high temperature gas phase method
Carbon material；
(2) under inert atmosphere protection, carbon material will be adulterated using ball-milling method and is mixed with silicon powder, it is multiple to obtain doped carbon/silicon
Condensation material.
2. the preparation method of doped carbon/silicon composite according to claim 1, spy is that the nitrogen source is NH3, phosphorus
Source is PH3, sulphur source H2S。
3. the preparation method of doped carbon/silicon composite according to claim 1 or 2, spy are the nitrogen source, phosphorus source
Or the volume fraction of sulphur source controls between 3 ~ 15%.
4. the preparation method of doped carbon/silicon composite according to claim 1, spy is that the carbon material is section's qin
One of black, super P, acetylene black, graphene, carbon nanotube.
5. the preparation method of doped carbon/silicon composite according to claim 1, spy be the doping carbon material/
The mass ratio of silicon powder controls between 1:1 ~ 1:9.
6. the preparation method of doped carbon/silicon composite according to claim 1, spy is that the high temperature gas phase method closes
At doping carbon material the step of it is as follows: in tube furnace, modification is doped to carbon material within the temperature range of 300 ~ 700 DEG C
2 ~ 6 hours.
7. the preparation method of doped carbon/silicon composite according to claim 1, spy is that the Ball-milling Time is greater than
36 hours, rotational speed of ball-mill was set as 400 ~ 750 r/min.
8. the preparation method of doped carbon/silicon composite according to claim 1, spy is that the inert gas is Ar
Or N2。
9. doped carbon/silicon composite that claim 1-8 any claim the method is prepared is as cathode in lithium
Application in ion battery and solid state battery.
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Cited By (4)
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| CN112652769A (en) * | 2020-12-21 | 2021-04-13 | 溧阳紫宸新材料科技有限公司 | Nonmetal element doped silica anode material and preparation method thereof |
| CN113690420A (en) * | 2021-08-26 | 2021-11-23 | 厦门大学 | Nitrogen-sulfur doped silicon-carbon composite material and preparation method and application thereof |
| CN113809311A (en) * | 2020-06-15 | 2021-12-17 | 溧阳天目先导电池材料科技有限公司 | Phosphorus-doped soft carbon-coated silicon-based lithium ion negative electrode material and preparation method and application thereof |
| CN114772595A (en) * | 2022-05-26 | 2022-07-22 | 中国农业科学院农业环境与可持续发展研究所 | Nitrogen-sulfur co-doped active biochar and preparation method thereof |
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Cited By (7)
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| CN113809311A (en) * | 2020-06-15 | 2021-12-17 | 溧阳天目先导电池材料科技有限公司 | Phosphorus-doped soft carbon-coated silicon-based lithium ion negative electrode material and preparation method and application thereof |
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| CN114772595A (en) * | 2022-05-26 | 2022-07-22 | 中国农业科学院农业环境与可持续发展研究所 | Nitrogen-sulfur co-doped active biochar and preparation method thereof |
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