CN108023084A - A kind of silicon-carbon cathode material preparation method and lithium ion battery - Google Patents
A kind of silicon-carbon cathode material preparation method and lithium ion battery Download PDFInfo
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- CN108023084A CN108023084A CN201711261229.0A CN201711261229A CN108023084A CN 108023084 A CN108023084 A CN 108023084A CN 201711261229 A CN201711261229 A CN 201711261229A CN 108023084 A CN108023084 A CN 108023084A
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- 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
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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 provides the preparation method and lithium ion battery of a kind of silicon-carbon cathode material, including：A catalyst precursor and carbon source) are subjected to chemical vapor deposition, obtain the catalyst of surface coated graphite alkene layer；B the catalyst of acid corrosion surface coated graphite alkene layer, isolated graphene cage material) are used；C) by graphene cage material and nano-silicon ball milling, it is dried to obtain persursor material；D) by persursor material and carbon source chemical vapor deposition, silicon-carbon cathode material is obtained.The present invention forms a thin layer of graphene in catalyst surface using chemical vapour deposition technique, removes catalyst, forms graphene basket structure；Nano-silicon is being deposited on inside graphene cage or surface, then is regarding agraphitic carbon cladding as buffer body and conductive agent, can effectively suppress dusting of the silicon in cyclic process, raising cycle performance.This preparation method is simple at the same time, and time-consuming short, and energy consumption is low, of low cost, environmentally protective.
Description
Technical field
The present invention relates to technical field of lithium ion battery negative, more particularly, to a kind of preparation of silicon-carbon cathode material
Method and its lithium ion battery.
Background technology
In the silica-base material studied at present, elemental silicon has higher specific capacity (4200mAh/g), embedding lithium due to it
The advantages such as current potential is low, thus widely paid close attention to.But it is unsatisfactory using silicon materials as battery material, it is primarily due to
Silicon is there are huge bulk effect during removal lithium embedded, and cubical expansivity is up to 400%, and the inside that volumetric expansion is brought should
Power causes silicon grain to be crushed in cyclic process, causes active material directly to come off from collector, capacity sharp-decay；Separately
Outside, silicon is a kind of semiconductor, electrical conductivity 2.52*10-4S/m, electric conductivity are very poor.
Existing research shows, silicon-carbon is compound be the current effective system for improving silicon system material volumetric expansion problem it
One.But still there are many problems demands to solve：Such as with carbon it is compound it is uneven, mutual combination power is weak, preparation method is complicated etc..
Silicon-carbon cathode material poor circulation that the prior art obtains, poorly conductive.In addition, the dusting that expansion is brought, directly results in appearance
Charge-discharge performance is poor under the rapid decay of amount, big multiplying power.
The content of the invention
In view of this, the technical problem to be solved in the present invention is the preparation method and lithium for providing a kind of silicon-carbon cathode material
Ion battery, the silicon-carbon cathode material that the present invention is prepared can effectively suppress dusting of the silicon in cyclic process, and raising follows
Ring performance and specific capacity.
The present invention provides a kind of preparation method of silicon-carbon cathode material, including：
A catalyst precursor and carbon source) are subjected to chemical vapor deposition, obtain the catalyst of surface coated graphite alkene layer；
B the catalyst of acid corrosion surface coated graphite alkene layer, isolated graphene cage material) are used；
C) by graphene cage material and nano-silicon ball milling, it is dried to obtain persursor material；
D) by persursor material and carbon source chemical vapor deposition, silicon-carbon cathode material is obtained.
Preferably, step A) catalyst precursor is selected from zinc oxide, magnesia, iron oxide, ferrous oxide, metal
One or more in iron, metallic zinc, metallic cobalt, metallic nickel, metallic copper and its alloy；
The carbon source is selected from methane, ethane, ethene, acetylene, benzene, pitch, phenolic resin, glucose, sucrose, starch, lemon
One or more in lemon acid and ascorbic acid.
Preferably, the step A) mass ratio of the catalyst precursor and carbon source is 1：2~2：1；The chemistry gas
Mutually the depositing temperature of deposition is 600~900 DEG C；The gasification temperature is 200~400 DEG C；The heating rate for 2~10 DEG C/
min；The chemical vapor deposition time is 1~4h.
Preferably, step B) one or more of the acid in hydrochloric acid, nitric acid and sulfuric acid；The sour mass concentration
Preferably 5%~30%.
Preferably, the step B) it is described with acid corrosion be under ultrasound condition, the ultrasonic time is 0.5~2h；Institute
Stating separation includes centrifuging and washing precipitation, drying；；The drying temperature is 50~80 DEG C；The drying time for 8~
12h。
Preferably, step C) mass ratio of the graphene cage material and nano-silicon is (60~80)：(40~20)；It is described
The particle diameter of nano-silicon is 1~100nm.
Preferably, step C) rotational speed of ball-mill is 300~600r/min；The ball milling is in inert gas or blanket of nitrogen
Enclose lower progress；The Ball-milling Time is 2~12h.
Preferably, step D) carbon source mass fraction that accounts for the persursor material is 5~25%；The chemical gaseous phase
The depositing temperature of deposition is 500~1000 DEG C；The gasification temperature is 300~600 DEG C；The heating rate for 2~10 DEG C/
min；The chemical vapor deposition time is 1~4h.
The present invention provides a kind of silicon-carbon cathode material, is prepared as the preparation method described in above-mentioned technical proposal.
The present invention provides a kind of lithium ion battery, its anode is as the negative material described in above-mentioned technical proposal and conduction
Agent, adhesive coated are in obtained on copper current collector.
Compared with prior art, the present invention provides a kind of preparation method of silicon-carbon cathode material, including：A) by catalyst
Presoma and carbon source carry out chemical vapor deposition, obtain the catalyst of surface coated graphite alkene layer；
B the catalyst of graphene layer, isolated graphene cage material) are coated with acid corrosion surface；
C) by graphene cage material and nano-silicon ball milling, it is dried to obtain persursor material；D) by persursor material and carbon source
Chemical vapor deposition, obtains silicon-carbon cathode material.The present invention is formed one layer thin using chemical vapour deposition technique in catalyst surface
Thin graphene, removes catalyst, forms graphene basket structure；Nano-silicon is being deposited on inside graphene cage or surface, then
Using agraphitic carbon cladding as buffer body and conductive agent, it can effectively suppress dusting of the silicon in cyclic process, improve cyclicity
Energy.This preparation method is simple at the same time, and time-consuming short, and energy consumption is low, of low cost, environmentally protective.
Brief description of the drawings
Fig. 1 is the cyclicity of lithium ion battery made from the silicon-carbon cathode material as anode prepared using the embodiment of the present invention 1
Can figure；
Fig. 2 is filling first for lithium ion battery made from the silicon-carbon cathode material as anode prepared using the embodiment of the present invention 2
Discharge curve；
Fig. 3 is filling first for lithium ion battery made from the silicon-carbon cathode material as anode prepared using the embodiment of the present invention 3
Discharge curve.
Embodiment
The present invention provides a kind of silicon-carbon cathode material preparation method and lithium ion battery, those skilled in the art can borrow
Reflect present disclosure, is suitably modified technological parameter realization.In particular, all similar substitutions and modifications are to this area
It is it will be apparent that they belong to the scope of protection of the invention for technical staff.The method and application of the present invention has been led to
Preferred embodiment is crossed to be described, related personnel substantially can not depart from present invention, in spirit and scope to this paper's
Methods and applications are modified or suitably change with combining, to realize and using the technology of the present invention.
The present invention provides a kind of preparation method of silicon-carbon cathode material, including：
A catalyst precursor and carbon source) are subjected to chemical vapor deposition, obtain the catalyst of surface coated graphite alkene layer；
B the catalyst of graphene layer, isolated graphene cage material) are coated with acid corrosion surface；
C) by graphene cage material and nano-silicon ball milling, it is dried to obtain persursor material；
D) by persursor material and carbon source chemical vapor deposition, silicon-carbon cathode material is obtained.
Catalyst precursor and carbon source are carried out chemical gas by the preparation method of silicon-carbon cathode material provided by the invention first
Mutually deposit, obtain the catalyst of surface coated graphite alkene layer.
Catalyst precursor of the present invention is preferably selected from zinc oxide, magnesia, iron oxide, ferrous oxide, metallic iron, gold
One or more in category zinc, metallic cobalt, metallic nickel and metallic copper and their alloy；
The carbon source is preferably selected from methane, ethane, ethene, acetylene, benzene, pitch, phenolic resin, glucose, sucrose, shallow lake
One or more in powder, citric acid and ascorbic acid；
Wherein, if gaseous carbon sources are used preferred coutroi velocity in 0.5L/min~4L/min.
The catalyst precursor and the mass ratio of carbon source are preferably 1：2~2：1.
Chemical vapor deposition of the present invention is chemical vapor deposition well known to those skilled in the art；It is preferred that in dual temperature area
Carried out in tube furnace.
The chemical vapor deposition is preferably specially：By catalyst precursor be placed on double temperature-area tubular furnaces high-temperature region and
Carbon source is placed on low-temperature space, and under the atmosphere of inert gas or nitrogen, high-temperature region rises to depositing temperature, and low-temperature space rises to gasification temperature
Degree, carries out chemical vapor deposition.
Wherein, the depositing temperature of the chemical vapor deposition is preferably 600~900 DEG C；The gasification temperature is preferably 200
~400 DEG C；The heating rate is preferably 2~10 DEG C/min；The chemical vapor deposition time is 1~4h.
Natural cooling must arrive the catalyst that surface is coated with graphene layer after chemical vapor deposition.
The catalyst of graphene layer, isolated graphene cage material are coated with acid corrosion surface.
It is preferred that it is specially：
The catalyst that above-mentioned surface is coated with to graphene layer adds acid according to solid-to-liquid ratio, and ultrasound, centrifuges and wash
Supernatant is precipitated to neutrality, is drying to obtain graphene cage material.
The solid-to-liquid ratio is preferably 1:10~1:100.One or more of the acid in hydrochloric acid, nitric acid and sulfuric acid；
The sour mass concentration is preferably 5%~30%.It is described with acid corrosion be under ultrasound condition, the ultrasonic time be 0.5
~2h；The drying temperature is 50~80 DEG C；The drying time is 8~12h.
Concrete mode of the invention for the centrifugation, washing is well known to those skilled in the art without limiting.
The cleaning solvent is preferably the one or more in ethanol and distilled water.
The present invention uses sour one side on the other hand can obtain graphene basket structure with catalyst-solvent.
By graphene cage material and nano-silicon ball milling, persursor material is dried to obtain.
The mass ratio of the graphene cage material and nano-silicon is preferably (60~80)：(40~20).The nano-silicon
Particle diameter is 1~100nm；More preferably 10~90nm.The drying is preferably to be spray-dried；The present invention is for the spray drying
Design parameter without limit, it is well known to those skilled in the art.
Specifically, the rotational speed of ball-mill is preferably 300~600r/min；The ball milling is in inert gas or nitrogen atmosphere
Lower progress；The Ball-milling Time is 2~12h；Preferably 2~10h.
The present invention is by graphene cage and nano-silicon ball milling, and most nano-silicon is deposited on the inside or surface of graphene cage at last.
As all include nano-silicon in inside cage and surface duct.
By persursor material and carbon source chemical vapor deposition, silicon-carbon cathode material is obtained.
It is preferred that it is specially：Persursor material is placed on to the high-temperature region of double temperature-area tubular furnaces, carbon source is placed on low-temperature space,
Under the atmosphere of inert gas or nitrogen, high-temperature region rises to depositing temperature, and low-temperature space rises to gasification temperature, carries out chemical vapor deposition
Product.Natural cooling after chemical vapor deposition to obtain the final product.
Wherein, the mass fraction that the carbon source accounts for the persursor material is preferably 5~25%；The chemical vapor deposition
Depositing temperature be 500~1000 DEG C；The gasification temperature is 300~600 DEG C；The heating rate is 2~10 DEG C/min；Institute
It is 1~4h to state the chemical vapor deposition time.
Unformed carbon source is coated on the graphene cage of inside or surface the deposition nano-silicon by the final present invention, is obtained
Silicon-carbon cathode material.
The present invention provides a kind of preparation method of silicon-carbon cathode material, including：A) by catalyst precursor and carbon source into
Row chemical vapor deposition, obtains the catalyst of surface coated graphite alkene layer；B the catalysis of acid corrosion surface coated graphite alkene layer) is used
Agent, isolated graphene cage material；C) by graphene cage material and nano-silicon ball milling, it is dried to obtain persursor material；D) will
Persursor material and carbon source chemical vapor deposition, obtain silicon-carbon cathode material.The present invention is being catalyzed using chemical vapour deposition technique
Agent surface forms a thin layer of graphene, removes catalyst, forms graphene basket structure；Nano-silicon is being deposited on graphene
Inside cage or surface, then agraphitic carbon is coated as buffer body and conductive agent, it can effectively suppress silicon in cyclic process
Dusting, improves cycle performance.This preparation method is simple at the same time, and time-consuming short, and energy consumption is low, of low cost, environmentally protective.
The present invention provides a kind of silicon-carbon cathode material, is prepared as the preparation method described in above-mentioned technical proposal.
Silicon-carbon cathode material provided by the invention, including internal or surface deposit the graphene cage of nano-silicon and are coated on institute
State the amorphous carbon layer on the graphene cage surface of internal or surface deposition nano-silicon.
Graphene of the present invention can improve the electric conductivity of material, graphene and agraphitic carbon and connection and support work are played to silicon
With can effectively alleviate volumetric expansion.
The present invention provides a kind of lithium ion battery, its anode is prepared into as the negative material described in above-mentioned technical proposal
Arrive.
In order to further illustrate the present invention, with reference to embodiments prepared by a kind of silicon-carbon cathode material provided by the invention
Method and lithium ion battery are described in detail.
Embodiment 1
Zinc oxide 1g, glucose 2g is taken to be individually positioned in high-temperature region and the low-temperature space of double temperature-area tubular furnaces, wherein high-temperature region
700 DEG C are risen to, low-temperature space rises to 350 DEG C, and heating rate is 2 DEG C/min, is passed through nitrogen chemical vapor deposition 1h and is wrapped up to surface
It is covered with the catalyst of graphene layer.
The hydrochloric acid of 50ml 5% is added in the above-mentioned 2.01g graphene coated Zinc oxide catalytics being prepared, is surpassed
Sound 0.5h, centrifugation, be precipitated to neutrality obtained by ethanol and distillation water washing centrifugation, and dry 12h is up to graphene cage at 60 DEG C.
Nano-silicon 0.6g and 0.9g graphene cage is added in ball grinder, under argon atmosphere, mixing and ball milling 300r/
Min ball millings 8h obtains slurry, then is spray-dried to obtain presoma；By above-mentioned gained presoma and account for above-mentioned gained forerunner weight
15% pitch be individually positioned in the high-temperature region of double temperature-area tubular furnaces and low-temperature space, wherein high-temperature region rise to 800 DEG C, low-temperature space
Rise to 400 DEG C, be passed through nitrogen chemical vapor deposition 1h to obtain the final product.
Fig. 1 is following for the lithium ion battery that the silicon-carbon cathode material prepared using the embodiment of the present invention 1 is assembled as anode
Ring performance map.Reversible specific capacity is 1236mAh/g first, and capacity retention ratio is after head effects circulate 200 times for 83.5%, 0.1C
98.8%.
Embodiment 2
Ormolu 2g, citric acid 2g is taken to be individually positioned in high-temperature region and the low-temperature space of double temperature-area tubular furnaces, its high temperature
Area rises to 900 DEG C, and low-temperature space rises to 400 DEG C, and heating rate is 10 DEG C/min, is passed through nitrogen chemical vapor deposition 2h up to surface
It is coated with the catalyst of graphene layer.
The nitric acid of 360ml 10% is added in the above-mentioned 3.6g graphene coated ormolu catalyst being prepared,
Ultrasonic 2h, centrifugation, be precipitated to neutrality obtained by ethanol and distillation water washing centrifugation, and dry 10h is up to graphene cage at 70 DEG C.
Nano-silicon 2.7g and 1.8g graphene cage is added in ball grinder, under argon atmosphere, mixing and ball milling 600r/
Min ball millings 2h obtains slurry, then is spray-dried to obtain presoma；By above-mentioned gained presoma and account for above-mentioned gained forerunner weight
25% phenolic resin be individually positioned in high-temperature region and the low-temperature space of double temperature-area tubular furnaces, wherein high-temperature region rises to 800 DEG C, low
Warm area rises to 200 DEG C, is passed through nitrogen chemical vapor deposition 2h to obtain the final product.
Fig. 2 is the head for the lithium ion battery that the silicon-carbon cathode material prepared using the embodiment of the present invention 2 is assembled as anode
Secondary charging and discharging curve figure.
Embodiment 3
Metallic nickel 5g, sucrose 2.5g is taken to be individually positioned in high-temperature region and the low-temperature space of double temperature-area tubular furnaces, wherein high-temperature region
600 DEG C are risen to, low-temperature space rises to 250 DEG C, and heating rate is 5 DEG C/min, is passed through nitrogen chemical vapor deposition 3h and is wrapped up to surface
It is covered with the catalyst of graphene layer.
The sulfuric acid of 350ml 15% is added in the above-mentioned 7.14g graphene coated metalNicatalysts being prepared,
Ultrasonic 1.5h, centrifugation, be precipitated to neutrality obtained by ethanol and distillation water washing centrifugation, and dry 8h is up to graphene at 80 DEG C
Cage.
Nano-silicon 0.9g and 2.1g graphene cage is added in ball grinder, under nitrogen atmosphere, mixing and ball milling 450r/
Min ball millings 3h obtains slurry, then is spray-dried to obtain presoma；Above-mentioned presoma is placed on to the high temperature of double temperature-area tubular furnaces
Area, wherein high-temperature region rise to 800 DEG C, are passed through methane gas chemical vapor deposition 2h to obtain the final product, the flow control of methane is in 3L/min.
Fig. 3 is the head for the lithium ion battery that the silicon-carbon cathode material prepared using the embodiment of the present invention 3 is assembled as anode
Secondary charging and discharging curve figure.
Comparative example one
Step 1.2 is as in the first embodiment, save step 3,600 DEG C of roastings under argon gas atmosphere in tube furnace by dried sample
Burn 1h to obtain the final product.
Comparative example two
Directly using the silica flour of 100nm as negative material assembled battery.
Using the material prepared by above-described embodiment 1~3 and comparative example 1~2 as active material, according to active material：It is conductive
Agent：The mass ratio of binding agent is (90~94):(1~3):(3~7), slurry is made by solvent of deionized water, coated on copper collection
On fluid, vacuum drying, wherein binding agent be that (the two mass ratio is 1 for butadiene-styrene rubber and carboxymethyl cellulose：1), conductive agent is
Carbon black or acetylene black, make lithium ion battery with traditional electrolyte and positive and negative anodes shell, test its chemical property.It is shown in Table 1,
The electrochemical property test knot for the lithium ion battery that table 1 is prepared for the negative material of the embodiment of the present invention 1~3 and comparative example 1~2
Fruit.
The electrochemical property test for the lithium ion battery that table 1 is prepared with the negative material of embodiment 1~3 and comparative example 1~2
As a result
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
- A kind of 1. preparation method of silicon-carbon cathode material, it is characterised in that including：A catalyst precursor and carbon source) are subjected to chemical vapor deposition, obtain the catalyst of surface coated graphite alkene layer；B the catalyst of acid corrosion surface coated graphite alkene layer, isolated graphene cage material) are used；C) by graphene cage material and nano-silicon ball milling, it is dried to obtain persursor material；D) by persursor material and carbon source chemical vapor deposition, silicon-carbon cathode material is obtained.
- 2. preparation method according to claim 1, it is characterised in that step A) catalyst precursor is selected from oxidation One kind in zinc, magnesia, iron oxide, ferrous oxide, metallic iron, metallic zinc, metallic cobalt, metallic nickel, metallic copper and its alloy It is or several；The carbon source is selected from methane, ethane, ethene, acetylene, carbon monoxide, benzene, pitch, phenolic resin, glucose, sucrose, shallow lake One or more in powder, citric acid and ascorbic acid.
- 3. preparation method according to claim 1, it is characterised in that the step A) catalyst precursor and carbon source Mass ratio be 1：2~2：1；The depositing temperature of the chemical vapor deposition is 600~900 DEG C；The gasification temperature for 200~ 400℃；The heating rate is 2~10 DEG C/min；The chemical vapor deposition time is 1~4h.
- 4. preparation method according to claim 1, it is characterised in that step B) acid is selected from hydrochloric acid, nitric acid and sulfuric acid In one or more；The sour mass concentration is preferably 5%~30%.
- 5. preparation method according to claim 1, it is characterised in that the step B) it is described with acid corrosion be in ultrasonic bar Under part, the ultrasonic time is 0.5~2h；The separation includes centrifuging and washing precipitation, drying；The drying temperature is 50~80 DEG C；The drying time is 8~12h.
- 6. preparation method according to claim 1, it is characterised in that step C) the graphene cage material and nano-silicon Mass ratio is (60~80)：(40~20)；The particle diameter of the nano-silicon is 1~100nm.
- 7. preparation method according to claim 1, it is characterised in that step C) rotational speed of ball-mill is 300~600r/ min；The ball milling is carried out under inert gas or nitrogen atmosphere；The Ball-milling Time is 2~12h.
- 8. preparation method according to claim 1, it is characterised in that step D) carbon source accounts for the persursor material Mass fraction is 5~25%；The depositing temperature of the chemical vapor deposition is 500~1000 DEG C；The gasification temperature for 300~ 600℃；The heating rate is 2~10 DEG C/min；The chemical vapor deposition time is 1~4h.
- 9. a kind of silicon-carbon cathode material, is prepared as the preparation method described in claim 1~8 any one.
- 10. a kind of lithium ion battery, it is characterised in that its anode is as the negative material system described in claim 1~8 any one It is standby to obtain.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114094104A (en) * | 2021-11-22 | 2022-02-25 | 青岛科技大学 | Sea urchin-shaped silicon-carbon composite material and preparation method and application thereof |
| CN114335533A (en) * | 2021-12-16 | 2022-04-12 | 珠海冠宇电池股份有限公司 | Negative electrode material and battery comprising same |
| CN114447284A (en) * | 2022-01-13 | 2022-05-06 | 东莞市无中有新能源科技有限公司 | Preparation method of graphene negative plate and lithium battery |
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| CN106082167A (en) * | 2016-06-13 | 2016-11-09 | 西南大学 | The carbon nano tube compound material of porous carbon supporting base end portion coated metal granule and the preparation method of derivant, product and application |
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| CN114094104A (en) * | 2021-11-22 | 2022-02-25 | 青岛科技大学 | Sea urchin-shaped silicon-carbon composite material and preparation method and application thereof |
| CN114335533A (en) * | 2021-12-16 | 2022-04-12 | 珠海冠宇电池股份有限公司 | Negative electrode material and battery comprising same |
| CN114335533B (en) * | 2021-12-16 | 2024-07-16 | 珠海冠宇电池股份有限公司 | Negative electrode material and battery comprising same |
| CN114447284A (en) * | 2022-01-13 | 2022-05-06 | 东莞市无中有新能源科技有限公司 | Preparation method of graphene negative plate and lithium battery |
| CN114447284B (en) * | 2022-01-13 | 2024-04-05 | 东莞市无中有新能源科技有限公司 | Preparation method of graphene negative plate and lithium battery |
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