CN106374088A - Method for preparing silicon/carbon composite material with magnesiothermic reduction process - Google Patents
Method for preparing silicon/carbon composite material with magnesiothermic reduction process Download PDFInfo
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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
- 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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- 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
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Abstract
The invention discloses a method for preparing a silicon/carbon composite material with a magnesiothermic reduction process, and belongs to the technical field of composite material preparation. The method comprises the following steps: (1) mixing a silicon dioxide source, an organic carbon source and a solvent, carrying out ball-milling to prepare a uniformly pulpous mixture, and obtaining a silicon dioxide-carbon precursor composite material through drying; (2) mixing the silicon dioxide-carbon precursor composite material with magnesium powder to carry out a magnesiothermic reduction reaction, collecting products and carrying out acid pickling and washing, and drying to obtain the silicon/carbon composite material. According to the method, silicon dioxide reduction and high temperature carbonization are completed by using a one-step process, and the method has the advantages of simple technical process, low cost and large-scale production; the prepared composite material effectively maintains the appearance of porous silicon, so that the composite material has preferable capability for bearing volumetric strain; the porous composite material is applied to a lithium battery, so that the lithium-ion de-intercalation depth is small, the ion diffusion path is short, the reversible capacity and coulombic efficiency of the lithium battery are effectively improved, and the cycle life is prolonged.
Description
Technical field
The invention belongs to technical field of composite preparation and in particular to one kind using magnesium reduction process prepare silicon-carbon be combined
The method of material.
Background technology
Lithium ion battery is widely used in various portable due to having high energy density and good cyclical stability
Formula electronic equipment.As the main storage lithium main body of lithium ion battery, in charge and discharge process, it realizes lithium ion to negative material
Embed and deviate from.In recent years, because traditional material with carbon element exists, specific capacity is low, first charge-discharge efficiency is low, organic solvent is embedding altogether
Enter etc. not enough, promote people to start the exploitation of the non-carbon material to other height ratio capacities.
Silicon materials in nature aboundresources, low price, what is more important silicon has very high theoretical capacity (can
Reach 4200mah/g), and as during lithium ion battery negative safer compared with graphite material the advantages of, thus receive research worker
Extensive concern it is considered to be graphite can be substituted as the negative material of lithium ion battery of future generation.
But serious change in volume (volumetric expansion 300%) can be produced in silicon materials charge and discharge process, not only make silicon material
Material produces serious efflorescence, also results in the position that sei film contacted with electrolyte in silicon and is continuously formed, thus leading to
The rapid decay of silicon electrode capacity in cyclic process.In addition, the electric conductivity of silicon is poor, hinder silicium cathode material high rate performance
Raising.In document, report adopts Composite, introduces good conductivity and the little activity/inactive formulation of bulk effect, and preparation is many
Phase composite materials, thus relaxing the bulk effect of silicon, improve the cycle performance of silicon-based anode.
At present, research work both domestic and external is concentrated mainly on the nanorize of silicon materials and prepares two sides of silicon based composite material
Face.Nano-silicon can effectively shorten lithium ion the evolving path, alleviate volumetric stress, improve its cyclical stability.As Tao Hua is superfine
(magnesium reduction process prepares porous silicon-carbon composite cathode material, silicate journal, the 8th phase of volume 41, in August, 2013) adopts two steps
Method is prepared for porous si/c composite.First porous silica is passed through magnesiothermic reduction, prepare porous silica material, then
Organic carbon source is injected in porous silicon internal holes and coats its surface, synthesize interlaced porous si/c of si, c and be combined
Material.The three kinds of porous si/c composites being prepared with sba-15, mcm-48 and kieselguhr for silicon source respectively are circulated 30 times
Reversible capacity afterwards is respectively 712,664 and 463ma h/g.This good stable circulation performance is mainly due to be combined
Loose structure in material can effectively alleviate the volumetric stress during silica-base material removal lithium embedded, and the addition of carbon can improve silicon
The electronic conductivity of sill, surface coated carbon can improve the compatibility of silica-base material and electrolyte, thus improving electricity
The stable circulation performance of pole material.
Find during practical study, due to needing after magnesiothermic reduction reaction that product is operated through overpickling, drying etc.
Easily change the pattern of porous silicon, and then affect the excellent properties of composite after carbon coating.
Content of the invention
The invention provides a kind of method preparing Si-C composite material using magnesium reduction process, reacted in magnesiothermic reduction
So that reducing silica and carbonization is carried out in journey simultaneously, simplify reactions steps, farthest keep porous silicon in composite
Pattern, improve Si-C composite material as lithium cell cathode material chemical property.
A kind of method preparing Si-C composite material using magnesium reduction process, comprises the following steps:
(1) silica source, organic carbon source and solvent are mixed, ball milling is obtained even paste mixture, and drying obtains two
Silicon oxide-carbon matrix precursor composite；
(2) silica-carbon forerunner's composite material is mixed with magnesium powder and carry out magnesiothermic reduction reaction, collect product and go forward side by side
Row pickling, washing, obtain described Si-C composite material after being dried.
Carbon source is first wrapped up silica source by the present invention, and in heating up process, the carbon source of outside parcel is carbonized, and rises
To more than 680 DEG C, magnesium vapor obtains porous silicon through carbon coating layer reduction silicon dioxide to temperature.The present invention one step completes silicon-carbon and is combined
The preparation of material, not only simplify operating procedure, and porous silicon surface cladding carbon can effectively stop subsequent technique such as pickling,
The impact to porous silicon pattern such as dry；In addition carbon coating layer limits the diffusion rate of internal magnesium vapor, improves turning of silicon
Rate.
Preferably, described silica source is kieselguhr, mesoporous silicon oxide or quartz.
Described organic carbon source is polymer, such as Kynoar, polypyrrole, tripolycyanamide, polyethylene glycol oxide,
In polyacrylonitrile, polystyrene, Polyethylene Glycol, polylactic acid, polycaprolactone and polymethyl methacrylate one or more
Mixture.
More preferably, described organic carbon source is Kynoar, polypyrrole, polyacrylonitrile or polystyrene.Such organic
Polymer substance viscosity is high, is easily wrapped in silica source surface.
Preferably, described silica source and organic carbon source mixing quality are than for 0.2:1～9:1.More preferably, it is described
The mixing quality of silica source and organic carbon source is than for 4～6:1.
In order that organic carbon source effectively wraps silica source, can be properly added solvent makes organic carbon source dissolve.Described
Solvent be toluene, chlorobenzene, dimethylbenzene, hexamethylene, methanol, ethanol, ethylene glycol, isopropanol, ether, expoxy propane, methyl acetate,
Any one in pyridine, oxolane, carbon tetrachloride, n- methyl pyrrolidone or two or more mixing.Preferably, institute
Stating solvent is n- methyl pyrrolidone or pyridine.
Preferably, the mixing quality of described organic carbon source and solvent is than for 1:1～1:5.More preferably, described organic carbon
The mixing quality of source and solvent is than for 1:1.
The present invention carries out raw material mixing using high-energy ball milling method, improves the mixed effect of raw material.Preferably, described ball milling
Rotating speed be 400～1000 revs/min, Ball-milling Time be 2～50 hours.More preferably, ratio of grinding media to material is 4～5:1, rotating speed is 700
Rev/min, Ball-milling Time is 4～6 hours.
In step (2), due to magnesium easy firing, silica-carbon forerunner's composite material is mixed with magnesium powder and reacts need to be
Carry out under non-oxidising gas atmosphere.Preferably, described non-oxygen atmosphere is nitrogen or argon.
Preferably, the mixing quality of described silica-carbon forerunner's composite material and magnesium powder is than for 1～2:1.More
Preferably, the mixing quality of described silica-carbon forerunner's composite material and magnesium powder is than for 1:1.
Preferably, the condition of described magnesiothermic reduction reaction: under non-oxygen atmosphere, to add under 5～20 DEG C of heating rate
Heat, to 680～700 DEG C, is incubated 4～6h.Preferably, magnesiothermic reduction temperature is 700 DEG C.
The acid that described pickling adopts is one or more of sulphuric acid, nitric acid, hydrochloric acid, Fluohydric acid., molar concentration is 0.1～
10mol/l.After pickling, deionized water and ethanol wash 3～5 times respectively, are dried in vacuum drying oven.
Present invention also offers a kind of Si-C composite material being prepared by said method.The content of silicon in composite
For 50～90%.
Present invention also offers a kind of lithium ion battery negative material, combined by active substance, conductive agent and binding agent, institute
Stating active substance is above-mentioned Si-C composite material.
It is demonstrated experimentally that the lithium ion battery initial charge specific capacity of ion cathode material lithium preparation provided by the present invention exists
More than 1200mah/g, after 100 circulations, capability retention is 90%, has reversible capacity height, coulombic efficiency height, circulation
The advantages of life-span length.
The beneficial effect that the present invention possesses:
(1) present invention completes reducing silica and high temperature cabonization using one-step method, process is simple, with low cost,
Can be mass-produced.
(2) pattern of porous silicon is effectively kept preferably to hold so as to have using the composite of the inventive method preparation
By volume adaptability to changes.
(3) composite porous it is applied to lithium battery so that lithium ion deintercalation depth is little, ion expands by prepared by the present invention
Scattered path is short, effectively increases reversible capacity, the coulombic efficiency of lithium battery, extends cycle life.
Brief description
Fig. 1 is the Raman spectrogram of the composite that embodiment 1 is obtained.
Fig. 2 is the charge-discharge test curve chart of the composite that embodiment 1 is obtained.
Fig. 3 is the composite charge-discharge test Performance comparision figure that embodiment 2 is obtained with comparative example 1.
Specific embodiment
With reference to specific embodiment, the invention will be further described.
Embodiment 1
1st, the preparation of Si-C composite material
Using planetary ball mill, kieselguhr, Kynoar and methyl pyrrolidone solvent are mixed with mass ratio 4:1:1
Close, ball material mass ratio is about 5:1, rotating speed is 400 revs/min, and Ball-milling Time obtains silicon dioxide/polyvinylidene fluoride alkenes after 4 hours
Even slurry material.The silicon dioxide obtaining/polyvinylidene fluoride alkenes homogenate material is placed in baking oven and dries.
Carry out composite according to 1:1 after taking-up and the ratio of magnesium powder is mixed.Mixture is placed in tube furnace,
It is heated to 700 DEG C with the heating rate of 5 DEG C/min in ar gas environment, be incubated 4 hours, naturally cool to room temperature；Carried out with hydrochloric acid
Pickling, then deionized water and ethanol washs 3 times respectively, drying at 100 DEG C in vacuum drying oven obtains silicon-carbon composite wood in 5 hours
Material.
Prepared Si-C composite material carries out Raman spectrum analyses, and result is as shown in Figure 1.
2nd, the preparation of Si-C composite material negative pole
Sample will be prepared by Si-C composite material (active material): conductive agent (conductive carbon black, super-p):
The mass ratio mixing of binding agent (Kynoar, pvdf)=8:1:1, adds a certain amount of n- methyl pyrrolidone (nmp) molten
Agent, using magnetic agitation mix homogeneously.Using coating machine, slurry is coated uniformly on Copper Foil, in vacuum drying oven 100 DEG C true
Empty be dried 10 hours, after through tabletting, cut into slices, be dried, weigh etc. and to obtain pole piece, battery to be assembled.
3rd, the preparation of lithium ion battery and test
Assembled battery in the glove box that the pole piece being dried is put into containing high-purity argon gas, in the button cell of assembling, just extremely
Si-C composite material, negative pole is lithium piece, and barrier film is polypropylene screen, and electrolyte is the lithium hexafluoro phosphate containing lithium salts for 1mol/l
(lipf6), solvent is the ethylene carbonate (ec) of 1:1:1: dimethyl carbonate (dmc): Ethyl methyl carbonate (emc) for volume ratio.
Using blue electrical measurement test system constant current, lithium ion battery is carried out with charge-discharge test, voltage tester scope is 0.01～1.5v.Result
As shown in Fig. 2 capacity after circulation 100 circle for the lithium battery is 1190mah/g, capability retention is 90%.
Embodiment 2
1st, the preparation of Si-C composite material
Using planetary ball mill by mesoporous silicon oxide, polypyrrole and pyridine solvent ball milling with mass ratio 6:1:1
Mixing, ball material mass ratio is about 4:1, and rotating speed is 700 revs/min, and Ball-milling Time obtains silicon dioxide/multi-metal polypyrrole after 6 hours even
Slurry material.The silicon dioxide obtaining/multi-metal polypyrrole homogenate material is placed in baking oven and dries.
Carry out composite according to 1:1 after taking-up and the ratio of magnesium powder carries out mixing material.Mixture is placed in tube furnace
In, it is heated to 700 DEG C with the heating rate of 5 DEG C/min in nitrogen environment, be incubated 5 hours, naturally cool to room temperature；Use hydrochloric acid
Carry out pickling, then deionized water and ethanol wash 3 times respectively, drying at 120 DEG C in vacuum drying oven obtains silicon-carbon for 3 hours again
Condensation material.
2nd, the preparation of Si-C composite material negative pole
Sample will be prepared by Si-C composite material (active material): conductive agent (conductive carbon black, super-p):
The mass ratio mixing of binding agent (Kynoar, pvdf)=8:1:1, adds a certain amount of n- methyl pyrrolidone (nmp) molten
Agent, using magnetic agitation mix homogeneously.Using coating machine, slurry is coated uniformly on Copper Foil, in vacuum drying oven 100 DEG C true
Empty be dried 10 hours, after through tabletting, cut into slices, be dried, weigh etc. and to obtain pole piece, battery to be assembled.
3rd, the preparation of lithium ion battery and test
Assembled battery in the glove box that the pole piece being dried is put into containing high-purity argon gas, in the button cell of assembling, just extremely
Si-C composite material, negative pole is lithium piece, and barrier film is polypropylene screen, and electrolyte is the lithium hexafluoro phosphate containing lithium salts for 1mol/l
(lipf6), solvent is the ethylene carbonate (ec) of 1:1:1: dimethyl carbonate (dmc): Ethyl methyl carbonate (emc) for volume ratio.
Using blue electrical measurement test system constant current, lithium ion battery is carried out with charge-discharge test, voltage tester scope is 0.01～1.5v.Result
As shown in Figure 3.
Comparative example 1
1st, the preparation of Si-C composite material
Mesoporous silicon oxide is mixed according to 1:1 with magnesium powder, mixture is placed in tube furnace, in nitrogen environment
It is heated to 700 DEG C with the heating rate of 5 DEG C/min, be incubated 5 hours, naturally cool to room temperature；Carry out pickling with hydrochloric acid, then spend
Ionized water and ethanol wash 3 times respectively, and drying at 120 DEG C in vacuum drying oven obtains for 3 hours.
Using planetary ball mill, porous silica material, polypyrrole and pyridine solvent ball milling are mixed with mass ratio 6:1:1
Close, ball material mass ratio is about 4:1, rotating speed is 700 revs/min, and Ball-milling Time obtains even slurry material after 6 hours.It is placed in baking oven
Dry, obtain Si-C composite material through 800 DEG C of calcining 2h.
2nd, the preparation of Si-C composite material negative pole
Sample will be prepared by Si-C composite material (active material): conductive agent (conductive carbon black, super-p):
The mass ratio mixing of binding agent (Kynoar, pvdf)=8:1:1, adds a certain amount of n- methyl pyrrolidone (nmp) molten
Agent, using magnetic agitation mix homogeneously.Using coating machine, slurry is coated uniformly on Copper Foil, in vacuum drying oven 100 DEG C true
Empty be dried 10 hours, after through tabletting, cut into slices, be dried, weigh etc. and to obtain pole piece, battery to be assembled.
3rd, the preparation of lithium ion battery and test
Assembled battery in the glove box that the pole piece being dried is put into containing high-purity argon gas, in the button cell of assembling, just extremely
Si-C composite material, negative pole is lithium piece, and barrier film is polypropylene screen, and electrolyte is the lithium hexafluoro phosphate containing lithium salts for 1mol/l
(lipf6), solvent is the ethylene carbonate (ec) of 1:1:1: dimethyl carbonate (dmc): Ethyl methyl carbonate (emc) for volume ratio.
Using blue electrical measurement test system constant current, lithium ion battery is carried out with charge-discharge test, voltage tester scope is 0.01～1.5v.Result
As shown in Figure 3.
As can be seen from Figure 3, the silicon carbon material cycle performance being obtained by first coating magnesiothermic reduction again is higher than first magnesium heat in bag
Cover process composite (circulation 100 circle).
The explanation of book according to the above description, those skilled in the art in the invention can also be carried out to above-mentioned embodiment
Suitable modifications and changes, therefore, all any modification, supplement or similar fashion made in the spirit of the present invention are replaced
Change, belong to the scope of protection of the invention.
Claims (10)
1. a kind of prepare the method for Si-C composite material it is characterised in that comprising the following steps using magnesium reduction process:
(1) silica source, organic carbon source and solvent are mixed, ball milling is obtained even paste mixture, and drying obtains titanium dioxide
Silico-carbo forerunner's composite material；
(2) silica-carbon forerunner's composite material is mixed with magnesium powder and carry out magnesiothermic reduction reaction, collect product and carry out acid
Wash, wash, after being dried, obtain described Si-C composite material.
2. the method for claim 1 it is characterised in that described silica source be kieselguhr, mesoporous silicon oxide or
Quartz.
3. the method for claim 1 is it is characterised in that described organic carbon source is Kynoar, polypyrrole, polypropylene
Nitrile or polystyrene.
4. the method for claim 1 is it is characterised in that described silica source with organic carbon source mixing quality ratio is
0.2:1～9:1.
5. the method for claim 1 it is characterised in that described organic carbon source and solvent mixing quality than for 1:1～
1:5.
6. the method for claim 1 is it is characterised in that the rotating speed of described ball milling is 400～1000 revs/min, during ball milling
Between be 2～50 hours.
7. the method for claim 1 is it is characterised in that described silica-carbon forerunner's composite material and magnesium powder
Mixing quality is than for 1～2:1.
8. method as claimed in claim 7 it is characterised in that described magnesiothermic reduction reaction condition: under non-oxygen atmosphere, with
It is heated to 680～700 DEG C under 5～20 DEG C of heating rate, be incubated 2～10h.
9. a kind of Si-C composite material by the preparation of claim 1-8 any one methods described.
10. a kind of lithium ion battery negative material, is combined it is characterised in that described work by active substance, conductive agent and binding agent
Property material be Si-C composite material as claimed in claim 9.
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| CN111244414A (en) * | 2020-01-16 | 2020-06-05 | 昆明理工大学 | Method for preparing silicon-carbon negative electrode material by magnesiothermic reduction |
| CN111936419A (en) * | 2018-02-28 | 2020-11-13 | 加利福尼亚大学董事会 | Silicon lithium ion electrode material |
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| US20220153597A1 (en) * | 2020-11-13 | 2022-05-19 | Clemson University | Hollow porous silicon-based structures and method of formation |
| CN114551886A (en) * | 2022-02-23 | 2022-05-27 | 湖北亿纬动力有限公司 | Composite negative electrode material, preparation method thereof and lithium ion battery |
| CN115763822A (en) * | 2023-01-06 | 2023-03-07 | 碳佳(北京)科技有限公司 | Silicon-carbon negative electrode composite material, application and lithium battery |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101609891A (en) * | 2007-07-27 | 2009-12-23 | 三星Sdi株式会社 | Si/C compound, negative active core-shell material and comprise its lithium battery |
| CN102969489A (en) * | 2012-12-05 | 2013-03-13 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material, preparation method of silicon-carbon composite material, and lithium ion battery containing silicon-carbon composite material |
| CN102208636B (en) * | 2011-05-12 | 2013-07-03 | 北京科技大学 | Method for preparing porous silicon/carbon composite material by using diatomite as raw material and application |
| CN104241620A (en) * | 2013-06-21 | 2014-12-24 | 国立大学法人蔚山科学技术大学校产学协力团 | Porous silicon based negative electrode active material, method for manufacturing the same, and rechargeable lithium battery including the same |
| CN104466185A (en) * | 2014-11-12 | 2015-03-25 | 中国科学院深圳先进技术研究院 | Silicon/carbon negative electrode composite material and preparation method thereof as well as lithium ion battery and negative electrode thereof |
| CN104900843A (en) * | 2015-06-13 | 2015-09-09 | 田东 | Preparation method of silicon carbon composite anode material |
| KR20150128432A (en) * | 2014-05-09 | 2015-11-18 | 주식회사 엘지화학 | Silicon-carbon composite, preparation method thereof, and anode active material comprising the same |
| CN105140487A (en) * | 2015-09-10 | 2015-12-09 | 中天储能科技有限公司 | Silicon carbon compound of negative electrode material of lithium ion battery and preparation method of silicon carbon compound |
| CN105845912A (en) * | 2016-05-15 | 2016-08-10 | 东北电力大学 | Method for porous silicon titanium dioxide composite negative electrode material of lithium ion battery by taking diatomite as raw material |
-
2016
- 2016-10-14 CN CN201610893698.3A patent/CN106374088A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101609891A (en) * | 2007-07-27 | 2009-12-23 | 三星Sdi株式会社 | Si/C compound, negative active core-shell material and comprise its lithium battery |
| CN102208636B (en) * | 2011-05-12 | 2013-07-03 | 北京科技大学 | Method for preparing porous silicon/carbon composite material by using diatomite as raw material and application |
| CN102969489A (en) * | 2012-12-05 | 2013-03-13 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material, preparation method of silicon-carbon composite material, and lithium ion battery containing silicon-carbon composite material |
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