CN108807869A - A kind of simple preparation method of silicon tin graphite alloy - Google Patents
A kind of simple preparation method of silicon tin graphite alloy Download PDFInfo
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- CN108807869A CN108807869A CN201810378939.XA CN201810378939A CN108807869A CN 108807869 A CN108807869 A CN 108807869A CN 201810378939 A CN201810378939 A CN 201810378939A CN 108807869 A CN108807869 A CN 108807869A
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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
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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
- H01M4/38—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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- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
Abstract
The present invention discloses a kind of simple preparation method of silicon tin graphite alloy, includes following steps：Include following steps：（1）Silica flour is uniformly mixed with glass putty：4-8g silica flours are added with 3-5g glass puttys in ball mill and are disperseed, argon gas is passed through and is protected, ball milling 15-25H, grinding rate 300-500rpm；Then 1-3g PVA and 0.3-0.7g graphite is added in the ball grinder of above-mentioned ball mill, in air ball milling 8-12H, grinding rate 300-500rpm；The weight ratio of mill ball and mixture is maintained at 10：1；（2）Anneal of material technique：Said mixture is put into tube furnace and is calcined, in argon atmosphere and 600-800 DEG C of temperature lower calcination 120-180 minutes, heating rate is 2-4 DEG C/min, is then cooled down with stove.By using the method for the present invention, first silica flour is uniformly mixed with glass putty, then carries out annealing process, it is simple for process highly stable silicon tin graphite alloy is made, and first charge-discharge capacity is high, and first charge discharge efficiency is also high, meets the needs used, is made and promotes the use of.
Description
Technical field
The present invention relates to chemical material preparation field technologies, refer in particular to a kind of simple preparation side of silicon tin graphite alloy
Method.
Background technology
Currently, lithium ion battery is since its high-energy density and good rate capability are applied to mobile phone, it is electronic
Vehicle, the every field such as laptop.In order to meet the application of requirements at the higher level, there is an urgent need to long circulation life and Fabrication of High Specific Capacitance
The new electrode materials of amount.In in the past few decades, commercialized graphite has been demonstrated to have in lithium ion battery good
Anode material, high stabilization capacity retention ratio is shown in cyclic process without significant capacity attenuation.However, theoretical
Capacity is low（372 mAh/g）Limit their extensive use.In order to develop high performance lithium ion battery, many research work
New effective anode material is had been achieved for, such as Si, Sn, Al and metal alloy.Wherein, due to the availability of silicon, mass ratio
Capacity（4200 mAh/g）With ideal de- lithium/intercalation potential（<0.5V vs. Li+）, silicon is considered as next-generation lithium-ion electric
One of most promising candidate in pond.However, two huge challenges that the business application of Si faces are the sheets in charge and discharge process
It is low big with volume expansion amount to levy electronic conductivity, causes mechanical stability poor, capacity attenuation is fast, and cycle life is short.
In order to alleviate serious volume change and improve the conductivity of Si simultaneously, permitted by coating Si with nano-sized carbon
More scientific researches.After carbon coating Si, performance（Such as electric conductivity, dispersibility, mechanical performance and chemical property）It has and significantly carries
It is high.In fact, since Si has high lithiumation ability, Si-C composite materials is made to cause prodigious concern, and carbonaceous material
Braced frame is may be used as to expand with buffer volumes and improve electron conduction.In addition, the embedded potential of approximation between Si and carbon
Contribute to the electrochemical stability of composite material.However, high-carbon content leads to the low capacity contribution to integral material.Although such as
This, high power capacity is prepared for LIBs, macrocyclic anode, and it is still a huge challenge to develop a kind of method of high performance-price ratio.
Invention content
In view of this, in view of the deficiencies of the prior art, the present invention aims to provide a kind of conjunctions of silicon cassiterite ink
The simple preparation method of gold, can synthesize highly stable silicon tin graphite alloy.
To achieve the above object, the present invention is using following technical solution：
A kind of simple preparation method of silicon tin graphite alloy, includes following steps：Include following steps：
（1）Silica flour is uniformly mixed with glass putty：4-8g silica flours are added with 3-5g glass puttys in ball mill and are disperseed, argon gas is passed through and is protected
Shield, ball milling 15-25H, grinding rate 300-500rpm；Then above-mentioned ball mill is added in 1-3g PVA and 0.3-0.7g graphite
Ball grinder in, ball milling 8-12H, grinding rate 300-500rpm in air；The weight ratio of mill ball and mixture is kept
10：1；
（2）Anneal of material technique：Said mixture is put into tube furnace and is calcined, at a temperature of argon atmosphere and 600-800 DEG C
Calcining 120-180 minutes, heating rate are 2-4 DEG C/min, are then cooled down with stove.
As a preferred embodiment, include following steps：
（1）Silica flour is uniformly mixed with glass putty：6g silica flours are added with 4g glass puttys in ball mill and are disperseed, argon gas is passed through and is protected,
Ball milling 20H, grinding rate 400rpm；Then 2g PVA and 0.5g graphite is added in the ball grinder of above-mentioned ball mill, in sky
Ball milling 10H in gas, grinding rate 400rpm；The weight ratio of mill ball and mixture is maintained at 10：1；
（2）Anneal of material technique：Said mixture is put into tube furnace and is calcined, in argon atmosphere and 700 DEG C of temperature lower calcinations
150 minutes, heating rate was 3 DEG C/min, is then cooled down with stove.
The present invention has clear advantage and advantageous effect compared with prior art, specifically, by above-mentioned technical proposal
Known to：
By using the method for the present invention, first silica flour is uniformly mixed with glass putty, then carries out annealing process, to be made highly stable
Silicon tin graphite alloy, it is simple for process, and first charge-discharge capacity is high, and first charge discharge efficiency is also high, meets the needs used, is made and pushes away
It is wide to use.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the Si/Sn@C-G composite materials obtained in the embodiment of the present invention 1；
Fig. 2 is that voltage is 0.01-2.5 V, 0.5C in the embodiment of the present invention 1（1C=1000 mA/g）Under the conditions of cyclicity for the first time
It can figure.
Specific implementation mode
Present invention is disclosed a kind of simple preparation methods of silicon tin graphite alloy, include following steps：Include following
Step：
（1）Silica flour is uniformly mixed with glass putty：4-8g silica flours are added with 3-5g glass puttys in ball mill and are disperseed, argon gas is passed through and is protected
Shield, ball milling 15-25H, grinding rate 300-500rpm；Then above-mentioned ball mill is added in 1-3g PVA and 0.3-0.7g graphite
Ball grinder in, ball milling 8-12H, grinding rate 300-500rpm in air；The weight ratio of mill ball and mixture is kept
10：1.
（2）Anneal of material technique：Said mixture is put into tube furnace and is calcined, in argon atmosphere and 600-800 DEG C of temperature
Degree lower calcining 120-180 minutes, heating rate is 2-4 DEG C/min, is then cooled down with stove.
With multiple embodiments, invention is further described in detail below：
Embodiment 1：
A kind of simple preparation method of silicon tin graphite alloy, includes following steps：
（1）Silica flour is uniformly mixed with glass putty：6g silica flours are added with 4g glass puttys in ball mill and are disperseed, argon gas is passed through and is protected,
Ball milling 20H, grinding rate 400rpm；Then 2g PVA and 0.5g graphite is added in the ball grinder of above-mentioned ball mill, in sky
Ball milling 10H in gas, grinding rate 400rpm；The weight ratio of mill ball and mixture is maintained at 10：1.
（2）Anneal of material technique：Said mixture is put into tube furnace and is calcined, at a temperature of argon atmosphere and 700 DEG C
Calcining 150 minutes, heating rate are 3 DEG C/min, are then cooled down with stove.
As shown in Figure 1, be the scanning electron microscope (SEM) photograph of the Si/Sn@C-G composite materials obtained in the present embodiment, institute as shown in Figure 1
Sample preparation product microscopic appearance is about 0.5um graininess aggregates.
The charge-discharge performance at different conditions that battery is tested by Land cell testers, as shown in Fig. 2, this implementation
Voltage is 0.01-2.5 V, 0.5C in example（1C=1000 mA/g）Under the conditions of cycle performance figure for the first time, for the first time discharge capacity be
1014.45mAh/g, initial charge capacity are 781.25mAh/g, and head effects are 77%.
Embodiment 2：
A kind of simple preparation method of silicon tin graphite alloy, includes following steps：Include following steps：
（1）Silica flour is uniformly mixed with glass putty：8g silica flours are added with 4g glass puttys in ball mill and are disperseed, argon gas is passed through and is protected,
Ball milling 16H, grinding rate 400rpm；Then 1g PVA and 0.4g graphite is added in the ball grinder of above-mentioned ball mill, in sky
Ball milling 9H in gas, grinding rate 400rpm；The weight ratio of mill ball and mixture is maintained at 10：1.
（2）Anneal of material technique：Said mixture is put into tube furnace and is calcined, at a temperature of argon atmosphere and 600 DEG C
Calcining 130 minutes, heating rate are 2 DEG C/min, are then cooled down with stove.
After tested, in the present embodiment, discharge capacity is 998.67mAh/g for the first time, and initial charge capacity is 739.02mAh/
G, head effect are 74%.
Embodiment 3：
A kind of simple preparation method of silicon tin graphite alloy, includes following steps：Include following steps：
（1）Silica flour is uniformly mixed with glass putty：7g silica flours are added with 3g glass puttys in ball mill and are disperseed, argon gas is passed through and is protected,
Ball milling 18H, grinding rate 350rpm；Then 2g PVA and 0.3g graphite is added in the ball grinder of above-mentioned ball mill, in sky
Ball milling 12H in gas, grinding rate 350rpm；The weight ratio of mill ball and mixture is maintained at 10：1.
（2）Anneal of material technique：Said mixture is put into tube furnace and is calcined, at a temperature of argon atmosphere and 650 DEG C
Calcining 128 minutes, heating rate are 4 DEG C/min, are then cooled down with stove.
After tested, in the present embodiment, discharge capacity is 990.87mAh/g for the first time, and initial charge capacity is 743.15mAh/
G, head effect are 75%.
Embodiment 4：
A kind of simple preparation method of silicon tin graphite alloy, includes following steps：Include following steps：
（1）Silica flour is uniformly mixed with glass putty：6g silica flours are added with 5g glass puttys in ball mill and are disperseed, argon gas is passed through and is protected,
Ball milling 15H, grinding rate 300rpm；Then 3g PVA and 0.6g graphite is added in the ball grinder of above-mentioned ball mill, in sky
Ball milling 10H in gas, grinding rate 450rpm；The weight ratio of mill ball and mixture is maintained at 10：1.
（2）Anneal of material technique：Said mixture is put into tube furnace and is calcined, at a temperature of argon atmosphere and 800 DEG C
Calcining 180 minutes, heating rate are 3 DEG C/min, are then cooled down with stove.
After tested, in the present embodiment, discharge capacity is 995.47mAh/g for the first time, and initial charge capacity is 716.74mAh/
G, head effect are 72%.
Embodiment 5：
A kind of simple preparation method of silicon tin graphite alloy, includes following steps：Include following steps：
（1）Silica flour is uniformly mixed with glass putty：5g silica flours are added with 4g glass puttys in ball mill and are disperseed, argon gas is passed through and is protected,
Ball milling 24H, grinding rate 450rpm；Then 2g PVA and 0.7g graphite is added in the ball grinder of above-mentioned ball mill, in sky
Ball milling 8H in gas, grinding rate 500rpm；The weight ratio of mill ball and mixture is maintained at 10：1.
（2）Anneal of material technique：Said mixture is put into tube furnace and is calcined, at a temperature of argon atmosphere and 720 DEG C
Calcining 175 minutes, heating rate are 2 DEG C/min, are then cooled down with stove.
After tested, in the present embodiment, discharge capacity is 990.61mAh/g for the first time, and initial charge capacity is 723.15mAh/
G, head effect are 73%.
Embodiment 6：
A kind of simple preparation method of silicon tin graphite alloy, includes following steps：Include following steps：
（1）Silica flour is uniformly mixed with glass putty：4g silica flours are added with 3g glass puttys in ball mill and are disperseed, argon gas is passed through and is protected,
Ball milling 25H, grinding rate 500rpm；Then 1g PVA and 0.5g graphite is added in the ball grinder of above-mentioned ball mill, in sky
Ball milling 9H in gas, grinding rate 420rpm；The weight ratio of mill ball and mixture is maintained at 10：1.
（2）Anneal of material technique：Said mixture is put into tube furnace and is calcined, at a temperature of argon atmosphere and 780 DEG C
Calcining 160 minutes, heating rate are 3 DEG C/min, are then cooled down with stove.
After tested, in the present embodiment, discharge capacity is 1000.23mAh/g for the first time, and initial charge capacity is 720.17mAh/
G, head effect are 72%.
The design focal point of the present invention is：By using the method for the present invention, first silica flour is uniformly mixed with glass putty, then carried out
Annealing process, it is simple for process highly stable silicon tin graphite alloy is made, and first charge-discharge capacity is high, first charge discharge efficiency
Also high, meet the needs used, is made and promotes the use of.
The above described is only a preferred embodiment of the present invention, be not intended to limit the scope of the present invention,
Therefore it is every according to the technical essence of the invention to any subtle modifications, equivalent variations and modifications made by above example, still
Belong in the range of technical solution of the present invention.
Claims (2)
1. a kind of simple preparation method of silicon tin graphite alloy, it is characterised in that：Include following steps：It include following step
Suddenly：
（1）Silica flour is uniformly mixed with glass putty：4-8g silica flours are added with 3-5g glass puttys in ball mill and are disperseed, argon gas is passed through and is protected
Shield, ball milling 15-25H, grinding rate 300-500rpm；Then above-mentioned ball mill is added in 1-3g PVA and 0.3-0.7g graphite
Ball grinder in, ball milling 8-12H, grinding rate 300-500rpm in air；The weight ratio of mill ball and mixture is kept
10：1；
（2）Anneal of material technique：Said mixture is put into tube furnace and is calcined, at a temperature of argon atmosphere and 600-800 DEG C
Calcining 120-180 minutes, heating rate are 2-4 DEG C/min, are then cooled down with stove.
2. a kind of simple preparation method of silicon tin graphite alloy according to claim 1, it is characterised in that：Include following
Step：
（1）Silica flour is uniformly mixed with glass putty：6g silica flours are added with 4g glass puttys in ball mill and are disperseed, argon gas is passed through and is protected,
Ball milling 20H, grinding rate 400rpm；Then 2g PVA and 0.5g graphite is added in the ball grinder of above-mentioned ball mill, in sky
Ball milling 10H in gas, grinding rate 400rpm；The weight ratio of mill ball and mixture is maintained at 10：1；
（2）Anneal of material technique：Said mixture is put into tube furnace and is calcined, in argon atmosphere and 700 DEG C of temperature lower calcinations
150 minutes, heating rate was 3 DEG C/min, is then cooled down with stove.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113690425A (en) * | 2021-10-26 | 2021-11-23 | 天津师范大学 | High-capacity silicon-based composite lithium battery negative electrode material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107749461A (en) * | 2016-08-22 | 2018-03-02 | 万向二三股份公司 | A kind of preparation method of carbon coating silicon tin composite negative plate |
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- 2018-04-25 CN CN201810378939.XA patent/CN108807869A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107749461A (en) * | 2016-08-22 | 2018-03-02 | 万向二三股份公司 | A kind of preparation method of carbon coating silicon tin composite negative plate |
Non-Patent Citations (1)
| Title |
|---|
| DANDAN YANG 等: "Simple synthesis of Si/Sn@C-G anodes with enhanced electrochemical properties for Li-ion batteries", 《ELECTROCHIMICA ACTA》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113690425A (en) * | 2021-10-26 | 2021-11-23 | 天津师范大学 | High-capacity silicon-based composite lithium battery negative electrode material and preparation method thereof |
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