CN109473665A - A kind of nano silica-base material and its preparation method and application - Google Patents
A kind of nano silica-base material and its preparation method and application Download PDFInfo
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- CN109473665A CN109473665A CN201811407016.9A CN201811407016A CN109473665A CN 109473665 A CN109473665 A CN 109473665A CN 201811407016 A CN201811407016 A CN 201811407016A CN 109473665 A CN109473665 A CN 109473665A
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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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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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
- H01M4/58—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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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Abstract
The invention discloses a kind of nano silica-base materials and its preparation method and application, preparation method is, the thick silicon and sulphur powder of business are first obtained into silicon sulfide through high temperature solid state reaction, it reacts silica progress metallothermic reduction to obtain nano-silicon, it is by ball milling that nano-silicon and sulfide solid electrolyte is compound again, obtain nano silica-base material.Compared with prior art, the advantages that present invention has energy consumption low, and cost is small, and the period is short, is conducive to large-scale production.And, nano-silicon is coated using amorphous sulfide solid electrolyte, prepare silicon/solid state electrolysis composite material, both volume change of silicon during lithiumation/de- lithiumation can have been buffered, it can prevent contact of the silicon particle with electrolyte again to inhibit silicon by electrolytic corrosion, and not influence diffusion of the lithium ion from liquid electrolyte to silicon particle.
Description
Technical field
The present invention relates to the technical fields of energy-storage battery, and in particular to a kind of nano silica-base material and preparation method thereof and answers
With.
Background technique
Lithium ion battery is widely used as mobile electronic device, such as smart phone, laptop now, and in electricity
Net energy storage, electric car field have huge market.But with lithium ion battery on electric car large-scale use,
Traditional graphite-based cathode is not able to satisfy the requirement of the growing high-energy density of power battery.Relative to graphite-based cathode, silicon
The theoretical capacity of base cathode reaches 4200mAh/g, with important application prospects.
But during forming Li-Si alloy, volume expansion is up to 300%, has seriously affected the cycle life of material.
Currently, improve silicium cathode cycle life measure mainly have: with carbon material it is compound, silicon particle size is down to nanoscale, formed
Porous structure.Although the cycle performance of silicon-based anode can be improved in nanosizing, Composite, the letter of nano silica-base material is realized
Single, prepare with scale still faces very big challenge.In addition, being different from graphite cathode, silicon-based anode is hardly formed stable SEI film,
Remaining HF also has corrosiveness to silicon in electrolyte, needs to carry out silicon certain surface protection, forms artificial SEI film.
Summary of the invention
It is an object of the present invention to provide a kind of nano silica-base material, the silica-base material by nanostructure silicon particle
Formed with the sulfide solid electrolyte of nanostructure, by by silicon nanosizing and with the Composite of solid electrolyte, can be effective
Improve the chemical property of silica-base material, especially cyclical stability.
It is also an object of the present invention to provide a kind of preparation methods of nano silica-base material, with the cheap thick silicon of business
It is presoma with sulphur, silicon sulfide is obtained by simple pyroreaction, is then obtained using simple metallothermic reduction porous
The size of thick silicon particle can be down to nanometer by micron order with the volume change during metallothermic reduction by vulcanizing by nano-silicon
Grade, then it is compound with solid electrolyte by simple ball-milling method, obtain nano-silicon/solid state electrolysis composite material.Utilize solid-state
The protective effect of electrolyte improves the stability of silicon-based anode.
It is another object of the present invention to provide a kind of nano silica-base materials in the application of lithium battery, has excellent electricity
Performance and cyclical stability.
Specific technical solution is as follows:
A kind of preparation method of nano silica-base material, comprising the following steps:
1) the thick silicon of business and sulphur are uniformly mixed, pyroreaction under inert atmosphere obtains silicon sulfide；
2) it by gained silicon sulfide and reducing metal and metal chloride ball milling in step 1), is uniformly mixed, obtains mixture；
3) mixture obtained by step 2) is placed in atmosphere protection stove, is passed through inert gas, carry out metallothermic reduction reaction,
Obtain metallothermic reduction product；
4) by after the pickling of metallothermic reduction product, drying obtained by step 3), nano-silicon is obtained；
5) nano-silicon obtained by step 4) is mixed with solid electrolyte, carries out ball milling, obtains nano silica-base material.
The molar ratio of sulphur described in step 1) and the thick silicon of business is 2.0~2.3:1；Preferably 2.05~2.1:1.
Further, pyroreaction temperature described in step 1) is 900~1300 DEG C, and the reaction time is 5~10 hours.It is excellent
Choosing, reaction temperature is 1000~1200 DEG C；
Further, inert atmosphere described in step 1) is argon gas, nitrogen or helium.
In step 1), uses the thick silicon of cheap business and sulphur powder for presoma, obtained using simple high temperature solid state reaction
Silicon sulfide.
In step 2), the reducing metal is magnesium metal, metallic aluminium or metallic zinc.
Further, the step 2) magnesium metal or metallic zinc and the molar ratio of silicon sulfide are 2~2.1:1, metallic aluminium with
The molar ratio of silicon sulfide is 4.0~4.3:3；
Further, the weight ratio of metal chloride described in step 2) and silicon sulfide is 5~10:1.The metal chlorine
Compound is the one or more of sodium chloride, potassium chloride, magnesium chloride, zinc chloride, aluminium chloride.
By the dosage of optimization reducing metal and metal chloride in step 2), going back completely for silicon sulfide is on the one hand realized
Original obtains of uniform size, well dispersed silicon nanoparticle, and can reduce the cost of preparation.
In step 3), the temperature of the metallothermic reduction reaction is 500~900 DEG C, and the time is 2~12 hours；It is preferred that
, the temperature of the metallothermic reduction reaction is 750~850 DEG C, and the time is 5~15 hours；
In step 3), by optimization metal fever reaction temperature and time, the complete reduction by silicon sulfide can have both been realized, improved
Yield avoids the cleaning of subsequent silicon sulfide or silicon sulfide from decomposing and generates silicon oxide impurity, and can reduce the reunion of silicon nanoparticle.
In step 4), the pickling refers to that 1mol/L hydrochloric acid cleans 12 hours.
Solid electrolyte dosage described in step 5) is the 5%~25% of nano-silicon quality.
Solid electrolyte described in step 5) is lithium sulfide and vulcanizes phosphate mixture, and the molar ratio of lithium sulfide and phosphoric sulfide is
0.5-0.9-0.5-0.1；Preferably 0.7-0.8:0.3-0.2.
Ball milling described in step 5) refers to that using concussion ball milling, frequency is 15~25Hz, and the time is 1~5 hour.Step 5)
It is excellent by optimization ball milling, it realizes in nano silicon particles coated with uniform amorphous sulfide solid electrolyte.
A kind of nano silica-base material provided by the invention, is prepared using the above method, the nano silica-base material by
Nano silicon particles and the sulfide solid electrolyte of nanostructure composition.By by silicon nanosizing and compound with solid electrolyte
Change, solid electrolyte is uniformly wrapped on silicon particle surface, forms core-shell structure, can effectively improve the electrochemistry of silica-base material
Can, special cyclical stability.
The sulfide solid electrolyte, molecular formula xLi2S(1–x)P2S5, wherein 0.5≤x≤0.9, it is preferred that 0.7≤
x≤0.8.Within this range, solid electrolyte has high lithium ion conductivity, is conducive to lithium ion from electrolyte to silicon particle
Diffusion.
Preferably, the sulfide solid electrolyte is amorphous state, and amorphous material is more advantageous in silicon particle surface shape
At fine and close protective film, contact of the silicon particle with electrolyte is inhibited to improve following for material to prevent corrosion of the silicon by electrolyte
Ring stability.Meanwhile being coated with for amorphous state solid-state electrolytic solution is conducive to inhibit volume change of the silicon in charge and discharge process, improves
The coulombic efficiency for the first time and cyclical stability of silica-base material.
Further, according to mass percent, the sulfide solid electrolyte quality is the 5% of nano silicon particles quality
~25%, it is preferred that 5%≤x≤10%.Within this range, be conducive to solid electrolyte and coat silicon particle completely, and formed
Nanostructure, and the diffusion of lithium ion is not hindered.Preferably, solid electrolyte is uniformly wrapped on silicon particle surface, core is formed
Shell structure.
Further, the size of the nano silicon particles is 10nm~500nm, it is preferred that the size of silicon particle is
50nm~200nm.Too small particle is unfavorable for the uniform cladding of solid electrolyte, too small particle also easily by electrolytic corrosion,
Excessive particle is unfavorable for the diffusion of lithium ion.
A kind of application the present invention also provides nano silica-base material in lithium battery has as lithium cell cathode material
Excellent electrical property and cyclical stability.
A kind of letter is provided for prepare with scale nano-silicon by reacting silica progress metallothermic reduction for nano-silicon
Folk prescription method can realize the crushing of feed particles by the stress of the volume change of metallothermic reduction reaction process, to be received
Rice silicon, further by and solid electrolyte it is compound, contact of the silicon particle with electrolyte can be prevented to reduce side reaction
Occur.
Compared with prior art, the present invention has the advantage that
1, the present invention uses the thick silicon of cheap business and sulphur for presoma, using high temperature solid state reaction and metal thermal response system
The advantages that standby nano-silicon, has energy consumption low, and cost is small, and the period is short, is conducive to large-scale production.
2, the present invention coats nano-silicon using amorphous sulfide solid electrolyte, prepares silicon/solid state electrolysis composite material,
Not only volume change of silicon during lithiumation/de- lithiumation can have been buffered, but also contact of the silicon particle with electrolyte can be prevented to inhibit
Silicon does not influence diffusion of the lithium ion from liquid electrolyte to silicon particle by electrolytic corrosion.
Detailed description of the invention
Fig. 1 is X-ray diffraction (XRD) map of nano silica-base material prepared by embodiment 1；
Fig. 2 is scanning electron microscope (SEM) photo of nano silicon material prepared by embodiment 1；
Fig. 3 is using nano silica-base material prepared by embodiment 1 as the charging and discharging curve of negative electrode of lithium ion battery.
Specific embodiment
Embodiment 1
A kind of preparation method of nano silica-base material, comprising the following steps:
1) first the thick silicon of business and sulphur powder are uniformly mixed by the molar ratio of 1:2.05, are sealed in quartz ampoule under an argon
In, then quartz ampoule is placed in tube furnace, is warming up to 1100 DEG C with 5 DEG C/min of speed, and heat preservation 10 is small at this temperature
When, obtain silicon sulfide；
2) then by the silicon sulfide of step 1) preparation and magnesium powder and sodium chloride through ball milling mixing, revolving speed 180r/min, ball
Time consuming is 10 hours, obtains mixture；The magnesium powder and the molar ratio of silicon sulfide are 2:1, belong to the weight of sodium chloride and silicon sulfide
Amount is than being 7:1.
3) the step 2) mixture is placed in tube furnace, is passed through argon gas, carry out magnesiothermic reduction reaction, reaction temperature is
800 DEG C, the reaction time is 10 hours；Reaction terminates, and is cooled to room temperature, and obtains magnesiothermic reduction reaction product；
4) by step 3) preparation magnesium thermit product through 1mol/L hydrochloric acid clean 12 hours, then with deionized water clean to
Neutrality obtains nano-silicon after dry；
5) mix nano-silicon obtained by step 4) with lithium sulfide and phosphoric sulfide (lithium sulfide and phosphoric sulfide molar ratio are 0.75:
0.25, wherein the sum of weight of lithium sulfide and phosphoric sulfide is the 10% of nano-silicon weight, carries out concussion ball milling and obtains silicon/sulfide
Composite material, the frequency for shaking ball milling is 20Hz, and Ball-milling Time is 3 hours, obtains nano silica-base material.
Product manufactured in the present embodiment is detected as the silicon of pure phase through XRD, and solid electrolyte does not exist since amorphous state is presented
Occur in diffraction maximum, sees Fig. 1.SEM shows that nano-silicon primary particle is 50~200nm, and surface is coated with uniform solid-state
Electrolyte layer is shown in Fig. 2.Superficial layer is sulfide through x-ray photoelectron spectrum analysis.
A kind of application of nano silica-base material in lithium battery, specific detection performance:
Using silicon based composite material manufactured in the present embodiment as anode, using lithium metal as cathode, Celgard2325 film be every
Film, LiPF6Ethylene carbonate (EC)/diethyl carbonate (DEC)/dimethyl carbonate (DMC) solution (volume ratio 1:1:1) be
Electrolyte assembles battery in the glove box full of argon gas, carries out charge-discharge test, and charging and discharging curve is as shown in Figure 3.Constant current
Charge-discharge test (current density 100mA/g, 0.005~2.5V of voltage range), from figure it is found that discharge capacity is up to 2960mAh/
G, for the first time coulombic efficiency 82%.
Comparative example 1
The preparation of nano silica-base material such as embodiment 1, difference are that the temperature of magnesium thermit in step 3) is 480 DEG C,
Reaction time is 10 hours.At this point, still there is more silicon sulfide in product, discharge capacity is lower than 700mAh/g, coulomb effect for the first time
Rate is lower than 50%.
Comparative example 2
The preparation of nano silica-base material such as embodiment 1, difference are that the temperature of magnesium thermit is 800 DEG C, the reaction time
It is 1.4 hours.At this point, still there is more silicon sulfide in product, discharge capacity is lower than 2000mAh/g for the first time, and coulombic efficiency is lower than
75%.
Comparative example 3
The preparation of nano silica-base material such as embodiment 1, difference are (not carry out step without introducing solid electrolyte
5)).At this point, discharge capacity is 3050mAh/g for the first time, coulombic efficiency is lower than 70%.
Comparative example 4
The preparation of nano silica-base material such as embodiment 1, difference do not introduce chlorination when being magnesium thermit in step 3)
Sodium.At this point, particle agglomeration, than more serious, discharge capacity is lower than 2900mAh/g for the first time, coulombic efficiency is lower than 80%.
Embodiment 2
A kind of preparation method of nano silica-base material, comprising the following steps:
1) first the thick silicon of business and sulphur powder are uniformly mixed by the molar ratio of 1:2.05, are sealed in quartz ampoule under an argon
In, then quartz ampoule is placed in tube furnace, is warming up to 1100 DEG C with 5 DEG C/min of speed, and heat preservation 10 is small at this temperature
When, it is cooled to room temperature, obtains silicon sulfide；
2) then by the silicon sulfide of step 1) preparation and aluminium powder and sodium chloride through ball milling mixing, revolving speed 180r/min, ball
Time consuming is 10 hours, obtains mixture；The molar ratio of aluminium powder and silicon sulfide is 4.0:3, the weight ratio of sodium chloride and silicon sulfide
For 6:1.
3) the step 2) mixture is placed in tube furnace, is passed through argon gas, carry out thermite reaction, reaction temperature is
750 DEG C, the reaction time is 15 hours；Reaction terminates, and is cooled to room temperature, and obtains thermite reaction product；
4) by step 3) preparation thermit reaction product through 1mol/L hydrochloric acid clean 12 hours, then with deionized water clean to
Neutrality obtains nano-silicon after dry；
5) mix nano-silicon obtained by step 4) with lithium sulfide and phosphoric sulfide (lithium sulfide and phosphoric sulfide molar ratio are 0.8:
0.2, wherein the sum of weight of lithium sulfide and phosphoric sulfide is the 8% of nano-silicon weight, and carrying out concussion ball milling, to obtain silicon/sulfide multiple
Condensation material, the frequency for shaking ball milling is 20Hz, and Ball-milling Time is 3 hours, obtains nano silica-base material.
The present embodiment product is detected as the silicon of pure phase through XRD, and solid electrolyte is due to being presented amorphous state.SEM shows
Nano-silicon primary particle is 50~200nm, and surface is coated with uniform solid-state electrolyte layer.
A kind of application of nano silica-base material in lithium battery, specific detection performance:
Using silicon based composite material manufactured in the present embodiment as anode, using lithium metal as cathode, Celgard2325 film be every
Film, LiPF6EC/DEC/DMC solution (volume ratio 1:1:1) be electrolyte, full of argon gas glove box in assemble battery,
Carry out charge-discharge test.Constant current charge-discharge test (current density 100mA/g, 0.005~2.5V of voltage range) shows electric discharge
Capacity is up to 2900mAh/g, coulombic efficiency 81% for the first time.
Embodiment 3
A kind of preparation method of nano silica-base material, comprising the following steps:
1) first the thick silicon of business and sulphur powder are uniformly mixed by the molar ratio of 1:2.05, are sealed in quartz ampoule under an argon
In, then quartz ampoule is placed in tube furnace, is warming up to 1100 DEG C with 5 DEG C/min of speed, and heat preservation 10 is small at this temperature
When, it is cooled to room temperature, obtains silicon sulfide；
2) then by the silicon sulfide of step 1) preparation and magnesium powder and potassium chloride through ball milling mixing, revolving speed 180r/min, ball
Time consuming is 10 hours, obtains mixture；Magnesium powder and the molar ratio of silicon sulfide are 2.2:3, the weight ratio of potassium chloride and silicon sulfide
For 9:1.
3) the step 2) mixture is placed in tube furnace, is passed through argon gas, carry out magnesiothermic reduction reaction, reaction temperature is
850 DEG C, the reaction time is 5 hours；Reaction terminates, and is cooled to room temperature, and obtains magnesiothermic reduction reaction product；
4) by step 3) preparation magnesium thermit product through 1mol/L hydrochloric acid clean 12 hours, then with deionized water clean to
Neutrality obtains nano-silicon after dry；
5) mix nano-silicon obtained by step 4) with lithium sulfide and phosphoric sulfide (lithium sulfide and phosphoric sulfide molar ratio are 0.7:
0.3, wherein the sum of weight of lithium sulfide and phosphoric sulfide is the 5% of nano-silicon weight, and carrying out concussion ball milling, to obtain silicon/sulfide multiple
Condensation material, the frequency for shaking ball milling is 20Hz, and Ball-milling Time is 3 hours, obtains nano silica-base material.
The present embodiment product is detected as the silicon of pure phase through XRD, and solid electrolyte is due to being presented amorphous state.SEM shows
Nano-silicon primary particle is 50~200nm, and surface is coated with uniform solid-state electrolyte layer.
A kind of application of nano silica-base material in lithium battery, specific detection performance:
Using silicon based composite material manufactured in the present embodiment as anode, using lithium metal as cathode, Celgard2325 film be every
Film, LiPF6EC/DEC/DMC solution (volume ratio 1:1:1) be electrolyte, full of argon gas glove box in assemble battery,
Carry out charge-discharge test.Constant current charge-discharge test (current density 100mA/g, 0.005~2.5V of voltage range) shows electric discharge
Capacity is up to 3050mAh/g, coulombic efficiency 81.5% for the first time.
Claims (10)
1. a kind of preparation method of nano silica-base material, which is characterized in that the preparation method comprises the following steps:
1) the thick silicon of business and sulphur are uniformly mixed, pyroreaction under inert atmosphere obtains silicon sulfide；
2) it by gained silicon sulfide and reducing metal and metal chloride ball milling in step 1), is uniformly mixed, obtains mixture；
3) mixture obtained by step 2) is placed in atmosphere protection stove, is passed through inert gas, carried out metallothermic reduction reaction, obtain
Metallothermic reduction product；
4) by after the pickling of metallothermic reduction product, drying obtained by step 3), nano-silicon is obtained；
5) nano-silicon obtained by step 4) is mixed with solid electrolyte, carries out ball milling, obtains nano silica-base material.
2. preparation method according to claim 1, which is characterized in that the molar ratio of sulphur described in step 1) and the thick silicon of business
For 2.0~2.3:1.
3. preparation method according to claim 1, which is characterized in that pyroreaction temperature described in step 1) be 900~
1300 DEG C, the reaction time is 5~10 hours.
4. preparation method according to claim 1-3, which is characterized in that the step 2) reducing metal is gold
Belong to magnesium, metallic aluminium or metallic zinc.
5. the preparation method according to claim 4, which is characterized in that the step 2) magnesium metal or metallic zinc and silicon sulfide
Molar ratio be 2~2.1:1, the molar ratio of metallic aluminium and silicon sulfide is 4.0~4.3:3；Metal chloride described in step 2)
Weight ratio with silicon sulfide is 5~10:1.
6. preparation method according to claim 1, which is characterized in that in step 3), the metallothermic reduction reaction
Temperature is 500~900 DEG C, and the time is 2~12 hours.
7. preparation method according to claim 1, which is characterized in that solid electrolyte dosage described in step 5) is nanometer
The 5%~25% of siliceous amount；The solid electrolyte is lithium sulfide and vulcanization phosphate mixture, the molar ratio of lithium sulfide and phosphoric sulfide
For 0.5-0.9-0.5-0.1.
8. preparation method according to claim 1 or claim 7, which is characterized in that ball milling described in step 5) refers to using concussion
Ball milling, frequency are 15~25Hz, and the time is 1~5.
9. a kind of nano silica-base material of any one of claim 1-8 the method preparation, which is characterized in that described nano silicon-based
Material is made of the sulfide solid electrolyte of nano silicon particles and nanostructure, and solid electrolyte is uniformly wrapped on silicon particle table
Face forms core-shell structure, the sulfide solid electrolyte, molecular formula xLi2S(1–x)P2S5, wherein 0.5≤x≤0.9, described
Sulfide solid electrolyte is amorphous state.
10. a kind of application of the nano silica-base material of any one of claim 1-8 the method preparation in terms of lithium battery.
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